Analytical Data

Synthesis of N-([1,1'-Biphenyl]-2-yl)acetamide (33aa)

The general procedure A was followed using 30a (135 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33aa (162 mg, 77%) as a colorless solid.

The general procedure B was followed using 30a (135 mg, 1.00 mmol) and hydroxydiphenylborane (76a) (273 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33aa (137 mg, 65%) as a colorless solid.

The general procedure C was followed using 30a (67.6 mg, 0.50 mmol) and potassium phenyltrifluoroborate (77a) (276 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33aa (55 mg, 52%) as a colorless solid.

M. p.: 113–115 °C.

1H-NMR (300 MHz, CDCl₃): δ = 8.21 (d, J = 8.2 Hz, 1H), 7.51‒7.30 (m, 6H), 7.24–7.13 (m, 3H), 1.98 (s, 3H).

13C-NMR (126 MHz, CDCl₃): δ = 168.2 (C_q), 138.1 (C_q), 134.6 (C_q), 132.2 (C_q), 130.0 (CH), 129.1 (CH), 129.0 (CH), 128.2 (CH), 127.9 (CH), 124.3 (CH), 121.7 (CH), 24.4 (CH₃).

IR (ATR): 3284, 3230, 3054, 3027, 1658, 1531, 1433, 1301, 755, 662 cm^‒1.

MS (EI) m/z (relative intensity): 211 ([M⁺] 34), 169 (100), 139 (7), 115 (5), 43 (15).

HR-MS (EI) m/z for C₁₄H₁₃NO [M⁺] calcd.: 211.0997.

found: 211.0996.

The analytical data are in accordance with those reported in the literature.^[163b]

Synthesis of N-([1,1'-Biphenyl]-2-yl)isobutyramide (33ba)

The general procedure A was followed using 30b (163 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ba (132 mg, 55%) as a colorless solid.

M. p.: 126–128 °C.

1H-NMR (300 MHz, CDCl3): δ = 8.33 (d, J = 8.2 Hz, 1H), 7.54‒7.33 (m, 6H), 7.28‒7.13 (m, 3H), 2.4 (hept, J = 6.8 Hz, 1H), 1.2 (d, J = 6.8 Hz, 6H).

13C-NMR (126 MHz, CDCl3): δ = 174.8 (Cq), 138.1 (Cq), 134.9 (Cq), 132.1 (Cq), 129.9 (CH), 129.3 (CH), 129.0 (CH), 128.4 (CH), 128.0 (CH), 124.0 (CH), 121.3 (CH), 36.7 (CH), 19.3 (CH3).

IR (ATR): 3218, 2964, 1649, 1520, 1480, 1239, 1203, 1099, 776, 542 cm^‒1. MS (EI) m/z (relative intensity): 239 ([M⁺] 29), 169 (100), 71 (6), 43 (30).

HR-MS (EI) m/z for C₁₆H₁₇NO [M⁺] calcd.: 239.1310.

found: 239.1314.

Synthesis of N-([1,1'-Biphenyl]-2-yl)pivalamide (33ca)

The general procedure A was followed using 30c (177 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ca (114 mg, 45%) as a colorless solid.

M. p.: 68–69 °C.

1H-NMR (300 MHz, CDCl₃): δ = 8.37 (dd, J = 8.2, 1.2 Hz, 1H), 7.54‒7.33 (m, 7H), 7.24 (dd, J = 7.4, 1.7 Hz, 1H), 7.17 (dd, J = 7.4, 1.7 Hz, 1H), 1.09 (s, 9H).

13C-NMR (126 MHz, CDCl3): δ = 176.1 (Cq), 138.0 (Cq), 135.0 (Cq), 132.0 (Cq), 129.6 (CH), 129.2 (CH), 128.9 (CH), 128.4 (CH), 127.9 (CH), 123.8 (CH), 120.8 (CH), 39.8 (Cq), 27.4 (CH3).

IR (ATR): 3259, 3056, 2970, 2904, 2868, 1646, 1503, 1477, 771, 647 cm^‒1. MS (EI) m/z (relative intensity): 253 ([M⁺] 53), 169 (60), 57 (100), 41 (17).

HR-MS (EI) m/z for C17H19NO [M⁺] calcd.: 253.1467.

found: 253.1472.

The analytical data are in accordance with those reported in the literature.^[170]

Synthesis of N-([1,1'-Biphenyl]-2-yl)-2,6-difluorobenzamide (33da)

The general procedure A was followed using 30d (233 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33da (93 mg, 30%) as a colorless solid.

M. p.: 127–128 °C.

1H-NMR (300 MHz, CDCl₃): δ = 8.48 (d, J = 8.0 Hz, 1H), 7.61 (s, 1H), 7.50‒7.17 (m, 9H), 6.90 (t, J = 8.2 Hz, 2H).

13C-NMR (126 MHz, CDCl₃): δ = 159.8 (C_q, JC‒F = 246.4, 6.7 Hz), 158.2 (C_q), 137.5 (C_q), 134.2 (Cq), 132.5 (Cq), 131.8 (CH, JC‒F = 10.3 Hz), 130.1 (CH), 129.3 (CH), 128.9 (CH), 128.4 (CH), 128.0 (CH), 124.9 (CH), 121.7 (CH), 114.4 (Cq, JC‒F = 19.6 Hz), 112.0 (CH, JC‒F = 20.5, 4.4 Hz).

19F-NMR (282 MHz, CDCl3): δ = -(111.85–112.02) (m).

IR (ATR): 3218, 3058, 3031, 1653, 1623, 1516, 1462, 1303, 1005, 741 cm^‒1.

MS (EI) m/z (relative intensity): 309 ([M⁺] 57), 167 (14), 141 (100), 113 (21), 63 (7).

HR-MS (EI) m/z for C19H13F2NO [M⁺] calcd.: 309.0965.

found: 309.0960.

Synthesis of N-(3-Methyl-[1,1'-biphenyl]-2-yl)acetamide (33ha)

The general procedure A was followed using 30h (149 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ha (76 mg, 34%) as a colorless solid.

M. p.: 125–127 °C.

1H-NMR (300 MHz, CDCl3): δ = 7.43‒7.30 (m, 5H), 7.29‒7.24 (m, 2H), 7.21‒7.14 (m, 1H), 6.64 (s, 1H), 2.31 (s, 3H), 2.00 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 169.4 (Cq), 139.7 (Cq), 139.6 (Cq), 136.9 (Cq), 132.6 (Cq), 130.2 (CH), 128.9 (CH), 128.4 (CH), 127.9 (CH), 127.5 (CH), 127.4 (CH), 23.0 (CH3), 18.5 (CH3).

IR (ATR): 3269, 3024, 2956, 2922, 1646, 1516, 1463, 1365, 1289, 790 cm^‒1. MS (EI) m/z (relative intensity): 225 ([M⁺] 36), 183 (100), 167 (31), 43 (26).

HR-MS (EI) m/z for C₁₅H₁₅NO [M⁺] calcd.: 225.1154.

found: 225.1146.

The analytical data are in accordance with those reported in the literature.^[29]

Synthesis of N-(4-Methyl-[1,1'-biphenyl]-2-yl)acetamide (33ia)

The general procedure A was followed using 30i (149 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ia (175 mg, 78%) as a colorless solid.

The general procedure C was followed using 30i (74.6 mg, 0.50 mmol) and potassium phenyltrifluoroborate (77a) (276 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ia (61 mg, 54%) as a colorless solid.

M. p.: 139–141 °C.

1H-NMR (300 MHz, CDCl₃): δ = 8.04 (s, 1H), 7.50‒7.28 (m, 5H), 7.21‒7.08 (m, 2H), 6.98 (d, J = 7.6 Hz, 1H), 2.38 (s, 3H), 1.98 (s, 3H).

13C-NMR (126 MHz, CDCl₃): δ = 168.0 (C_q), 138.3 (C_q), 138.1 (C_q), 134.3 (C_q), 129.7 (CH), 129.4 (C_q), 129.2 (CH), 128.9 (CH), 127.6 (CH), 125.1 (CH), 122.2 (CH), 24.6 (CH₃), 21.5 (CH₃).

IR (ATR): 3224, 3029, 2916, 1652, 1539, 1476, 1412, 1297, 820, 763 cm^‒1. MS (EI) m/z (relative intensity): 225 ([M⁺] 54), 183 (100), 167 (30), 43 (20).

HR-MS (EI) m/z for C15H15NO [M⁺] calcd.: 225.1154.

found: 225.1159.

Synthesis of N-(5-Methyl-[1,1'-biphenyl]-2-yl)acetamide (33ja)

The general procedure A was followed using 30j (149 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ja (178 mg, 79%) as a colorless solid.

M. p.: 107–109 °C.

1H-NMR (300 MHz, CDCl3): δ = 8.06 (d, J = 8.3 Hz, 1H), 7.50‒7.31 (m, 5H), 7.16 (dd, J = 8.3, 2.2 Hz, 1H), 7.04 (m, 2H), 2.33 (s, 3H), 1.99 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 168.0 (Cq), 138.3 (Cq), 134.0 (Cq), 132.3 (Cq), 132.0 (Cq), 131.0 (CH), 129.1 (CH), 128.9 (CH), 128.8 (CH), 127.7 (CH), 121.9 (CH), 24.5 (CH3), 20.9 (CH3).

IR (ATR): 3235, 3057, 3029, 2922, 1655, 1524, 1505, 1488, 1366, 761 cm^‒1. MS (EI) m/z (relative intensity): 225 ([M⁺] 54), 183 (100), 167 (18), 43 (22).

HR-MS (EI) m/z for C15H15NO [M⁺] calcd.: 225.1154.

found: 225.1154.

The analytical data are in accordance with those reported in the literature.^[163b]

Synthesis of N-(5-Ethyl-[1,1'-biphenyl]-2-yl)acetamide (33ka)

The general procedure A was followed using 30k (163 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ka (151 mg, 63%) as a colorless solid.

M. p.: 64–65 °C.

1H-NMR (300 MHz, CDCl3): δ = 8.07 (d, J = 8.3 Hz, 1H), 7.54‒7.31 (m, 5H), 7.20 (dd, J = 8.3, 2.3 Hz, 1H), 7.13 (s, 1H), 7.09 (d, J = 2.3 Hz, 1H), 2.65 (q, J = 7.6 Hz, 2H), 2.00 (s, 3H), 1.25 (t, J = 7.6 Hz, 3H).

13C-NMR (126 MHz, CDCl3): δ = 168.0 (Cq), 140.3 (Cq), 138.3 (Cq), 132.5 (Cq), 132.1 (Cq), 129.3 (CH), 129.0 (CH), 128.8 (CH), 127.6 (CH), 127.5 (CH), 122.2 (CH), 28.3 (CH2), 24.4 (CH3), 15.6 (CH3).

IR (ATR): 3267, 3027, 2964, 2930, 2871, 1659, 1513, 1487, 1297, 767 cm^‒1.

MS (EI) m/z (relative intensity): 239 ([M⁺] 58), 197 (58), 182 (100), 180 (19), 167 (16), 43 (37).

HR-MS (EI) m/z for C₁₆H₁₇NO [M⁺] calcd.: 239.1310.

found: 239.1306.

Synthesis of N-(5-Methoxy-[1,1'-biphenyl]-2-yl)acetamide (33la)

The general procedure A was followed using 30l (165 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 1/1) yielded 33la (183 mg, 76%) as a colorless solid.

M. p.: 112–114 °C.

1H-NMR (300 MHz, CDCl₃): δ = 7.95 (d, J = 8.9 Hz, 1H), 7.50‒7.28 (m, 5H), 6.98 (s, 1H), 6.88 (dd, J = 8.9, 3.0 Hz, 1H), 6.78 (d, J = 3.0 Hz, 1H), 3.78 (s, 3H), 1.97 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 168.2 (Cq), 156.3 (Cq), 138.1 (Cq), 134.7 (Cq), 128.9 (CH), 128.8 (CH), 127.8 (CH), 127.6 (Cq), 124.3 (CH), 115.3 (CH), 113.3 (CH), 55.5 (CH3), 24.2 (CH3).

IR (ATR): 3263, 3058, 2969, 2939, 2838, 1664, 1480, 1270, 1178, 701 cm^‒1.

MS (EI) m/z (relative intensity): 241 ([M⁺] 71), 199 (76), 184 (100), 154 (21), 128 (11), 43 (34).

HR-MS (EI) m/z for C15H15NO2 [M⁺] calcd.: 241.1103.

found: 241.1106.

The analytical data are in accordance with those reported in the literature.^[163b]

Synthesis of N-(4-Methoxy-[1,1'-biphenyl]-2-yl)acetamide (33ma)

The general procedure A was followed using 30m (165 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ma (174 mg, 72%) as a colorless solid.

The general procedure C was followed using 30m (82.6 mg, 0.50 mmol) and potassium phenyltrifluoroborate (77a) (276 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ma (64 mg, 53%) as a colorless solid.

M. p.: 91–93 °C.

1H-NMR (300 MHz, CDCl₃): δ = 7.98 (d, J = 2.6 Hz, 1H), 7.49‒7.42 (m, 2H), 7.40‒7.36 (m, 1H), 7.35‒7.29 (m, 2H), 7.17 (s, 1H), 7.12 (d, J = 8.5 Hz, 1H), 6.72 (dd, J = 8.5, 2.6 Hz, 1H), 3.84 (s, 3H), 2.00 (s, 3H).

13C-NMR (126 MHz, CDCl₃): δ = 168.1 (Cq), 159.4 (C_q), 137.9 (C_q), 135.6 (C_q), 130.6 (CH), 129.3 (CH), 129.0 (CH), 127.6 (CH), 124.2 (Cq), 110.5 (CH), 106.2 (CH), 55.5 (CH3), 24.8 (CH3).

IR (ATR): 3241, 3033, 2953, 2831, 1652, 1309, 1233, 762, 724, 698 cm^‒1.

MS (EI) m/z (relative intensity): 241 ([M⁺] 74), 199 (100), 170 (16), 156 (19), 84 (9), 43 (34).

HR-MS (EI) m/z for C15H15NO2 [M⁺] calcd.: 241.1103.

found: 241.1107.

The analytical data are in accordance with those reported in the literature.^[27]

Synthesis of N-(2-Phenylnaphthalen-1-yl)acetamide (33na)

The general procedure A was followed using 30n (185 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33na (76 mg, 29%) as a colorless solid.

M. p.: 135–136 °C.

1H-NMR (300 MHz, CDCl₃): δ = 8.01‒7.90 (m, 2H), 7.70‒7.28 (m, 10H), 2.13 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 173.7 (Cq), 139.0 (Cq), 138.3 (Cq), 133.9 (Cq), 132.8 (Cq), 130.6 (Cq), 129.7 (CH), 128.7 (CH), 128.5 (CH), 128.4 (CH), 128.3 (CH), 128.2 (CH), 128.1 (CH), 126.7 (CH), 122.1 (CH), 26.2 (CH3).

IR (ATR): 3059, 2955, 2923, 2853, 1700, 1364, 1223, 994, 826, 760 cm^‒1. MS (EI) m/z (relative intensity): 261 ([M⁺] 61), 219 (100), 43 (19).

HR-MS (EI) m/z for C18H15NO [M⁺] calcd.: 261.1154.

found: 261.1153.

The analytical data are in accordance with those reported in the literature.^[171]

Synthesis of N-([1,1':3',1''-Terphenyl]-4'-yl)acetamide (33oa)

The general procedure A was followed using 30o (211 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33oa (155 mg, 54%) as a colorless solid.

M. p.: 114–115 °C.

1H-NMR (300 MHz, CDCl3): δ = 8.34 (d, J = 8.5 Hz, 1H), 7.63‒7.55 (m, 3H), 7.54‒7.36 (m, 8H), 7.33 (d, J = 7.2 Hz, 1H), 7.17 (s, 1H), 2.03 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 168.3 (Cq), 140.4 (Cq), 138.2 (Cq), 137.2 (Cq), 134.1 (Cq), 132.6 (Cq), 129.3 (CH), 129.2 (CH), 128.8 (CH), 128.7 (CH), 128.2 (CH), 127.3 (CH), 127.0 (CH), 126.9 (CH), 121.9 (CH), 24.5 (CH3).

IR (ATR): 3289, 3029, 2925, 1651, 1503, 1478, 760, 694, 649, 598 cm^‒1. MS (EI) m/z (relative intensity): 287 ([M⁺] 46), 245 (100), 43 (19).

HR-MS (EI) m/z for C₂₀H₁₇NO [M⁺] calcd.: 287.1310.

found: 287.1316.

Synthesis of N-(5-Hydroxy-[1,1'-biphenyl]-2-yl)acetamide (33pa)

The general procedure A was followed using 30p (151 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 3/7) yielded 33pa (157 mg, 69%) as a pale yellow viscous oil.

1H-NMR (300 MHz, CDCl3): δ = 7.59 (d, J = 9.5 Hz, 1H), 7.53 (s, 1H), 7.43‒7.32 (m, 3H), 7.30‒7.24 (m, 2H), 7.05 (s, 1H), 6.73‒6.67 (m, 2H), 1.99 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 169.7 (Cq), 154.1 (Cq), 138.1 (Cq), 136.1 (Cq), 128.8 (CH), 128.6 (CH), 127.6 (CH), 126.0 (Cq), 125.7 (CH), 117.1 (CH), 115.3 (CH), 23.9 (CH3).

IR (ATR): 3268, 3057, 2959, 2795, 1524, 1488, 1433, 1299, 1199, 726 cm^‒1. MS (EI) m/z (relative intensity): 227 ([M⁺] 44), 185 (100), 154 (11), 43 (14).

HR-MS (EI) m/z for C₁₄H₁₃NO₂ [M⁺] calcd.: 227.0946.

found: 227.0945.

Synthesis of N-(5-Fluoro-[1,1'-biphenyl]-2-yl)acetamide (33qa)

The general procedure A was followed using 30q (153 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33qa (163 mg, 71%) as a colorless solid.

M. p.: 131–133 °C.

1H-NMR (300 MHz, CDCl3): δ = 8.20‒8.05 (m, 1H), 7.59‒7.28 (m, 5H), 7.17‒6.88 (m, 3H), 2.00 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 168.1 (Cq), 159.1 (Cq, JC‒F = 244.1 Hz), 137.0 (Cq, JC‒F = 1.5 Hz), 134.4 (Cq, JC‒F = 7.7 Hz), 130.6 (Cq, JC‒F = 2.9 Hz), 129.0 (CH), 128.9 (CH), 128.3 (CH), 123.9 (CH, JC‒F = 8.1 Hz), 116.5 (CH, JC‒F = 22.9 Hz), 114.8 (CH, JC‒F = 21.8 Hz), 24.4 (CH3).

19F-NMR (282 MHz, CDCl3): δ = -(117.76–118.03) (m).

IR (ATR): 3274, 3238, 3031, 1659, 1533, 1483, 1410, 1180, 871, 771 cm^‒1.

MS (EI) m/z (relative intensity): 229 ([M⁺] 34), 187 (100), 104 (14), 84 (14), 43 (21).

HR-MS (EI) m/z for C₁₄H₁₂FNO [M⁺] calcd.: 229.0903.

found: 229.0904.

The analytical data are in accordance with those reported in the literature.^[163b]

Synthesis of N-(5-Chloro-[1,1'-biphenyl]-2-yl)acetamide (33ra)

The general procedure A was followed using 30r (169 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ra (165 mg, 67%) as a colorless solid.

M. p.: 126–127 °C.

1H-NMR (300 MHz, CDCl3): δ = 8.20 (d, J = 8.8 Hz, 1H), 7.50‒7.39 (m, 3H), 7.34‒7.27 (m, 3H), 7.20 (d, J = 2.5 Hz, 1H), 7.10 (s, 1H), 1.98 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 168.0 (Cq), 136.7 (Cq), 133.6 (Cq), 133.2 (Cq), 129.6 (CH), 129.3 (Cq), 129.1 (CH), 128.9 (CH), 128.3 (CH), 128.1 (CH), 122.8 (CH), 24.5 (CH3).

IR (ATR): 3257, 3188, 3029, 1647, 1520, 1390, 1367, 820, 767, 699 cm^‒1.

MS (EI) m/z (relative intensity): 245 ([M⁺] 36), 203 (100), 167 (44), 139 (12), 43 (34).

HR-MS (EI) m/z for C14H12ClNO [M⁺] calcd.: 245.0607.

found: 245.0604.

The analytical data are in accordance with those reported in the literature.^[163b]

Synthesis of N-(5-Bromo-[1,1'-biphenyl]-2-yl)acetamide (33sa)

The general procedure A was followed using 30s (214 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33sa (182 mg, 63%) as a colorless solid.

M. p.: 127–128 °C.

1H-NMR (300 MHz, CDCl3): δ = 8.21 (d, J = 8.7 Hz, 1H), 7.55‒7.43 (m, 4H), 7.41‒7.30 (m, 3H), 7.08 (s, 1H), 2.01 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 168.2 (Cq), 136.8 (Cq), 134.0 (Cq), 133.9 (Cq), 132.7 (CH), 131.3 (CH), 129.4 (CH), 129.1 (CH), 128.6 (CH), 123.0 (CH), 116.9 (Cq), 24.5 (CH3).

IR (ATR): 3278, 3055, 3025, 1651, 1515, 1386, 1369, 768, 700, 672 cm^‒1.

MS (EI) m/z (relative intensity): 289 ([M⁺] 31), 247 (100), 167 (71), 139, (23), 84 (20), 43 (32).

HR-MS (EI) m/z for C₁₄H₁₂BrNO [M⁺] calcd.: 289.0102.

found: 289.0103.

The analytical data are in accordance with those reported in the literature.^[163b]

Synthesis of Methyl 6-acetamido-[1,1'-biphenyl]-3-carboxylate (33ta)

The general procedure A was followed using 30t (193 mg, 1.00 mmol) and phenylboronic acid (73a) (183 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ta (156 mg, 58%) as a colorless solid.

M. p.: 136–137 °C.

1H-NMR (300 MHz, CDCl3): δ = 8.46 (d, J = 8.7 Hz, 1H), 8.01 (dd, J = 8.7, 2.1 Hz, 1H), 7.90 (d, J = 2.1 Hz, 1H), 7.54‒7.40 (m, 3H), 7.38‒7.34 (m, 2H), 7.31 (s, 1H), 3.87 (s, 3H), 2.02 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 168.1 (Cq), 166.4 (Cq), 138.8 (Cq), 136.9 (Cq), 131.4 (CH), 131.0 (Cq), 130.0 (CH), 129.3 (CH), 129.1 (CH), 128.4 (CH), 125.3 (Cq), 120.0 (CH), 52.1 (CH3), 24.9 (CH3).

IR (ATR): 3358, 3030, 2949, 1711, 1679, 1585, 1511, 1296, 1106, 770 cm^‒1.

MS (EI) m/z (relative intensity): 269 ([M⁺] 49), 227 (100), 196 (92), 167 (29), 43 (21).

HR-MS (EI) m/z for C₁₆H₁₅NO₃ [M⁺] calcd.: 269.1052.

found: 269.1056.

Synthesis of N-(4'-Methyl-[1,1'-biphenyl]-2-yl)acetamide (33ab)

The general procedure A was followed using 30a (135 mg, 1.00 mmol) and p-tolylboronic acid (73b) (204 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ab (185 mg, 82%) as a colorless solid.

The general procedure B was followed using 30a (135 mg, 1.00 mmol) and hydroxydi-p-tolylborane (76b) (315 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ab (133 mg, 59%) as a colorless solid.

The general procedure C was followed using 30a (67.6 mg, 0.50 mmol) and potassium p-tolyltrifluoroborate (77b) (297 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ab (71 mg, 63%) as a colorless solid.

M. p.: 106–108 °C.

1H-NMR (300 MHz, CDCl3): δ = 8.24 (d, J = 8.2 Hz, 1H), 7.44‒7.06 (m, 8H), 2.41 (s, 3H), 2.01 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 168.0 (Cq), 137.6 (Cq), 135.0 (Cq), 134.6 (Cq), 132.0 (Cq), 130.0 (CH), 129.7 (CH), 128.9 (CH), 128.1 (CH), 124.1 (CH), 121.4 (CH), 24.6 (CH3), 21.2 (CH3).

IR (ATR): 3340, 2956, 2921, 2853, 1515, 1442, 1282, 817, 756, 680 cm^‒1. MS (EI) m/z (relative intensity): 225 ([M⁺] 55), 183 (100), 167 (37), 43 (26).

HR-MS (EI) m/z for C₁₅H₁₅NO [M⁺] calcd.: 225.1154.

found: 225.1149.

The analytical data are in accordance with those reported in the literature.^[27]

Synthesis of N-{2-(Naphthalen-2-yl)phenyl}acetamide (33ac)

The general procedure A was followed using 30a (135 mg, 1.00 mmol) and naphthalen-2-ylboronic acid (73c) (258 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ac (167 mg, 64%) as a colorless solid.

M. p.: 131–132 °C.

1H-NMR (300 MHz, CDCl3): δ = 8.30 (d, J = 8.2 Hz, 1H), 8.00‒7.82 (m, 4H), 7.61‒7.53 (m, 2H), 7.49 (dd, J = 8.4, 1.7 Hz, 1H), 7.41 (td, J = 7.8, 1.7 Hz, 1H), 7.35 (d, J = 6.8 Hz, 1H), 7.28‒7.12 (m, 2H), 1.99 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 168.3 (Cq), 135.5 (Cq), 134.9 (Cq), 133.5 (Cq), 132.6 (Cq), 132.1 (Cq), 130.2 (CH), 128.7 (CH), 128.5 (CH), 128.3 (CH), 128.0 (CH), 127.8 (CH), 127.0 (CH), 126.7 (CH), 126.6 (CH), 124.4 (CH), 121.8 (CH), 24.6 (CH3).

IR (ATR): 3261, 3053, 3025, 1643, 1522, 1443, 1368, 1275, 856, 817 cm^‒1. MS (EI) m/z (relative intensity): 261 ([M⁺] 47), 219 (100), 189 (14), 43 (17).

HR-MS (EI) m/z for C₁₈H₁₅NO [M⁺] calcd.: 261.1154.

found: 261.1153.

The analytical data are in accordance with those reported in the literature.^[172]

Synthesis of N-(4'-Methoxy-[1,1'-biphenyl]-2-yl)acetamide (33ad)

The general procedure A was followed using 30a (135 mg, 1.00 mmol) and p-methoxyphenylboronic acid (73d) (228 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ad (200 mg, 83%) as a colorless solid.

The general procedure B was followed using 30a (135 mg, 1.00 mmol) and hydroxybis(4-methoxyphenyl)borane (76d) (363 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ad (150 mg, 62%) as a colorless solid.

The general procedure C was followed using 30a (67.6 mg, 0.50 mmol) and potassium p-methoxyphenyltrifluoroborate (77d) (321 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ad (64 mg, 53%) as a colorless solid.

M. p.: 135–137 °C.

1H-NMR (300 MHz, CDCl3): δ = 8.20 (d, J = 8.2 Hz, 1H), 7.34‒7.24 (m, 3H), 7.23‒7.09 (m, 3H), 6.98 (d, J = 8.6 Hz, 2H), 3.84 (s, 3H), 2.00 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 168.3 (Cq), 159.3 (Cq), 134.8 (Cq), 132.0 (Cq), 130.3 (CH), 130.2 (Cq), 130.1 (CH), 128.0 (CH), 124.3 (CH), 121.6 (CH), 114.4 (CH), 55.2 (CH3), 24.4 (CH3).

IR (ATR): 3351, 3012, 2921, 2842, 1690, 1439, 1239, 1175, 832, 770 cm^‒1.

MS (EI) m/z (relative intensity): 241 ([M⁺] 54), 199 (100), 184 (37), 154 (24), 128 (12), 43 (30).

HR-MS (EI) m/z for C₁₅H₁₅NO₂ [M⁺] calcd.: 241.1103.

found: 241.1110.

The analytical data are in accordance with those reported in the literature.^[27]

Synthesis of N-{2-(Benzo[d][1,3]dioxol-5-yl)phenyl}acetamide (33ae)

The general procedure A was followed using 30a (135 mg, 1.00 mmol) and benzo[d][1,3]dioxol-5-ylboronic acid (73e) (249 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ae (174 mg, 68%) as a colorless solid.

M. p.: 111–112 °C.

1H-NMR (300 MHz, CDCl₃): δ = 8.25 (d, J = 8.2 Hz, 1H), 7.37‒7.30 (m, 1H), 7.24‒7.08 (m, 3H), 6.91 (dd, J = 7.6, 0.8 Hz, 1H), 6.85‒6.77 (m, 2H), 6.03 (s, 2H), 2.04 (s, 3H).

13C-NMR (126 MHz, CDCl₃): δ = 168.3 (Cq), 148.3 (C_q), 147.5 (C_q), 134.9 (C_q), 131.8 (C_q), 131.7 (C_q), 130.1 (CH), 128.3 (CH), 124.2 (CH), 122.6 (CH), 121.5 (CH), 109.7 (CH), 108.8 (CH), 101.3 (CH₂), 24.6 (CH₃).

IR (ATR): 3320, 2890, 1668, 1522, 1445, 1224, 1032, 927, 807, 756 cm^‒1.

MS (EI) m/z (relative intensity): 255 ([M⁺] 65), 213 (100), 182 (13), 154 (34), 127 (12), 43 (30).

HR-MS (EI) m/z for C15H13NO3 [M⁺] calcd.: 255.0895.

found: 255.0901.

Synthesis of N-(4'-Bromo-[1,1'-biphenyl]-2-yl)acetamide (33af)

The general procedure A was followed using 30a (135 mg, 1.00 mmol) and p-bromophenylboronic acid (73f) (301 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33af (183 mg, 63%) as a colorless solid.

M. p.: 138–139 °C.

1H-NMR (400 MHz, CDCl3): δ = 8.05 (d, J = 8.2 Hz, 1H), 7.57‒7.53 (m, 2H), 7.32 (ddd, J = 8.5, 6.5, 2.5 Hz, 1H), 7.23‒7.11 (m, 5H), 1.97 (s, 3H).

13C-NMR (126 MHz, CDCl₃): δ = 168.4 (C_q), 137.2 (C_q), 134.4 (C_q), 132.1 (CH), 131.8 (C_q), 130.8 (CH), 129.9 (CH), 128.6 (CH), 124.8 (CH), 122.7 (CH), 122.1 (Cq), 24.1 (CH3).

IR (ATR): 3262, 3056, 3028, 1651, 1524, 1445, 1283, 1070, 826, 758 cm^‒1.

MS (EI) m/z (relative intensity): 289 ([M⁺] 29), 247 (100), 167 (65), 139 (18), 43 (29).

HR-MS (EI) m/z for C₁₄H₁₂BrNO [M⁺] calcd.: 289.0102.

found: 289.0104.

The analytical data are in accordance with those reported in the literature.^[173]

Synthesis of N-(4'-Chloro-[1,1'-biphenyl]-2-yl)acetamide (33ag)

The general procedure A was followed using 30a (135 mg, 1.00 mmol) and p-chlorophenylboronic acid (73g) (235 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ag (172 mg, 70%) as a colorless solid.

M. p.: 114–116 °C.

1H-NMR (300 MHz, CDCl3): δ = 8.16 (d, J = 8.2 Hz, 1H), 7.46‒7.40 (m, 2H), 7.39‒7.32 (m, 1H), 7.31‒7.26 (m, 2H), 7.20‒7.17 (m, 2H), 7.01 (s, 1H), 2.01 (s, 3H).

13C-NMR (126 MHz, CDCl₃): δ = 168.1 (C_q), 136.5 (C_q), 134.4 (C_q), 134.0 (C_q), 131.3 (C_q), 130.5 (CH), 129.9 (CH), 129.1 (CH), 128.6 (CH), 124.6 (CH), 122.2 (CH), 24.6 (CH3).

IR (ATR): 3247, 3031, 2924, 2854, 1635, 1527, 1369, 1283, 1086, 828 cm^‒1.

MS (EI) m/z (relative intensity): 245 ([M⁺] 35), 203 (100), 167 (43), 139 (12), 84 (17), 43 (36).

HR-MS (EI) m/z for C14H12ClNO [M⁺] calcd.: 245.0607.

found: 245.0599.

The analytical data are in accordance with those reported in the literature.^[172]

Synthesis of N-(3',4',5'-Trifluoro-[1,1'-biphenyl]-2-yl)acetamide (33ah)

The general procedure A was followed using 30a (135 mg, 1.00 mmol) and (3,4,5-trifluorophenyl)boronic acid (73h) (264 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ah (180 mg, 68%) as a colorless solid.

M. p.: 140–141 °C.

1H-NMR (300 MHz, CDCl₃): δ = 8.08 (d, J = 8.1 Hz, 1H), 7.40 (ddd, J = 8.5, 5.9, 3.1 Hz, 1H), 7.24‒7.17 (m, 2H), 7.06‒6.97 (m, 2H), 6.93 (s, 1H), 2.07 (s, 3H).

13C-NMR (126 MHz, CDCl₃): δ = 168.1 (Cq), 151.4 (C_q, J_C-F = 251.6, 10.0, 4.2 Hz), 139.5 (Cq, JC-F = 253.1, 15.0 Hz), 134.6 (Cq), 134.5 (Cq), 130.5 (Cq), 129.8 (CH), 129.5 (CH), 125.1 (CH), 123.3 (CH), 113.5 (CH, JC-F = 16.1, 5.4 Hz), 24.3 (CH3).

19F-NMR (282 MHz, CDCl3): δ = -(132.8‒133.0) (m), -161.0 (tt, JC-F = 20.6, 6.5 Hz).

IR (ATR): 3263, 3040, 2934, 2864, 1660, 1526, 1483, 1359, 872, 762 cm^‒1.

MS (EI) m/z (relative intensity): 265 ([M⁺] 29), 223 (100), 203 (16), 175 (5), 169 (5), 84 (6), 43 (41).

HR-MS (EI) m/z for C₁₄H₁₀F₃NO [M⁺] calcd.: 265.0714.

found: 265.0718.

Synthesis of N-(3',4'-Dichloro-5-fluoro-[1,1'-biphenyl]-2-yl)acetamide (33qi)

The general procedure A was followed using 30q (153 mg, 1.00 mmol) and (3,4-dichlorophenyl)boronic acid (73i) (286 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 6/4) yielded 33qi (188 mg, 63%) as a colorless solid.

M. p.: 146–148 °C.

1H-NMR (300 MHz, CDCl3): δ = 8.02‒7.94 (m, 1H), 7.53 (d, J = 8.2 Hz, 1H), 7.44 (d, J = 2.0 Hz, 1H), 7.18 (dd, J = 8.2, 2.1 Hz, 1H), 7.12‒7.01 (m, 1H), 6.96‒6.93 (m, 2H), 2.02 (s, 3H).

13C-NMR (75 MHz, CDCl₃): δ = 168.5 (C_q), 159.5 (C_q, J_C-F = 246.4 Hz), 137.2 (C_q, J_C-F = 1.6 Hz ), 133.3 (C_q), 133.0 (C_q, J_C-F = 7.6 Hz), 132.8 (C_q), 131.0 (CH), 130.9 (CH), 130.4 (C_q, J_C-F = 2.7 Hz), 128.2 (CH), 125.4 (CH, J_C-F = 8.0 Hz), 116.5 (CH, J_C-F = 23.2 Hz), 115.7 (CH, J_C-F = 21.9 Hz), 24.2 (CH₃).

19F-NMR (282 MHz, CDCl3): δ = -116.6 (s).

IR (ATR): 3242, 3190, 1652, 1529, 1472, 1371, 1183, 863, 702, 685 cm^‒1.

MS (EI) m/z (relative intensity): 297 ([M⁺] 48), 255 (100), 219 (40), 185 (52), 157 (17), 43 (60).

HR-MS (EI) m/z for C14H10Cl2FNO [M⁺] calcd.: 297.0123.

found: 297.0128.

The analytical data are in accordance with those reported in the literature.^[32]

Synthesis of N-(4,4'-Dimethyl-[1,1'-biphenyl]-2-yl)acetamide (33ib)

The general procedure B was followed using 30i (149 mg, 1.00 mmol) and hydroxydi-p-tolylborane (76b) (315 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33ib (146 mg, 61%) as a colorless solid.

M. p.: 120–121 °C.

1H-NMR (500 MHz, CDCl₃): δ = 8.06 (s, 1H), 7.28‒7.20 (m, 4H), 7.15 (s, 1H), 7.10 (d, J = 7.7 Hz, 1H), 6.96 (d, J = 7.7 Hz, 1H), 2.40 (s, 3H), 2.38 (s, 3H), 1.99 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 168.1 (Cq), 138.1 (Cq), 137.4 (Cq), 135.1 (Cq), 134.4 (Cq), 129.8 (CH), 129.6 (CH), 129.3 (Cq), 129.1 (CH), 125.1 (CH), 122.1 (CH), 24.5 (CH3), 21.4 (CH3), 21.1 (CH3).

IR (ATR): 3621, 3304, 3274, 1663, 1538, 1479, 1291, 812, 608, 530 cm^‒1. MS (EI) m/z (relative intensity): 239 ([M⁺] 76), 197 (100), 181 (29), 43 (31).

HR-MS (EI) m/z for C16H17NO [M⁺] calcd.: 239.1310.

found: 239.1311.

Synthesis of N-(4-Methoxy-4'-methyl-[1,1'-biphenyl]-2-yl)acetamide (33mb)

The general procedure B was followed using 30m (165 mg, 1.00 mmol) and hydroxydi-p-tolylborane (76b) (315 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33mb (163 mg, 64%) as a colorless solid.

M. p.: 82–83 °C.

1H-NMR (500 MHz, CDCl₃): δ = 7.97 (s, 1H), 7.28‒7.18 (m, 5H), 7.10 (d, J = 8.4 Hz, 1H), 6.69 (dd, J = 8.6, 2.7 Hz, 1H), 3.82 (s, 3H), 2.39 (s, 3H), 2.00 (s, 3H).

13C-NMR (126 MHz, CDCl₃): δ = 168.1 (Cq), 159.4 (C_q), 137.4 (C_q), 135.7 (C_q), 134.9 (C_q), 130.6 (CH), 129.7 (CH), 129.2 (CH), 124.2 (Cq), 110.4 (CH), 106.2 (CH), 55.4 (CH3), 24.7 (CH3), 21.1 (CH3).

IR (ATR): 3330, 2965, 1668, 1581, 1475, 1419, 1305, 1235, 1041, 803 cm^‒1. MS (EI) m/z (relative intensity): 255 ([M⁺] 77), 213 (100), 170 (32), 43 (29).

HR-MS (EI) m/z for C16H17NO2 [M⁺] calcd.: 255.1259.

found: 255.1257.

Synthesis of N-(4',5-Dimethyl-[1,1'-biphenyl]-2-yl)acetamide (33hb)

The general procedure B was followed using 30h (149 mg, 1.00 mmol) and hydroxydi-p-tolylborane (76b) (315 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33hb (151 mg, 63%) as a colorless solid.

The general procedure C was followed using 30h (74.6 mg, 0.50 mmol) and potassium p-tolyltrifluoroborate (77b) (297 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33hb (66 mg, 55%) as a colorless solid.

M. p.: 97–98 °C.

1H-NMR (500 MHz, CDCl3): δ = 8.06 (d, J = 8.4 Hz, 1H), 7.27‒7.21 (m, 4H), 7.13 (dd, J = 8.4, 2.1 Hz, 1H), 7.09 (s, 1H), 7.03 (s, 1H), 2.40 (s, 3H), 2.32 (s, 3H), 1.99 (s, 3H).

13C-NMR (126 MHz, CDCl3): δ = 168.1 (Cq), 137.6 (Cq), 135.3 (Cq), 133.9 (Cq), 132.3 (Cq), 132.1 (Cq), 130.6 (CH), 129.6 (CH), 129.0 (CH), 128.7 (CH), 121.8 (CH), 24.4 (CH3), 21.1 (CH3), 20.8 (CH3).

IR (ATR): 3365, 3025, 2922, 2865, 1673, 1509, 1290, 815, 731, 667 cm^‒1. MS (EI) m/z (relative intensity): 239 ([M⁺] 63), 197 (100), 180 (39), 43 (29).

HR-MS (EI) m/z for C₁₆H₁₇NO [M⁺] calcd.: 239.1310.

found: 239.1312.

Synthesis of N-(5-Methoxy-4'-methyl-[1,1'-biphenyl]-2-yl)acetamide (33lb)

The general procedure B was followed using 30l (165 mg, 1.00 mmol) and hydroxydi-p-tolylborane (76b) (315 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33lb (156 mg, 61%) as a colorless solid.

The general procedure C was followed using 30l (82.6 mg, 0.50 mmol) and potassium p-tolyltrifluoroborate (77b) (297 mg, 1.50 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 33lb (72 mg, 56%) as a colorless solid.

M. p.: 109–110 °C.

1H-NMR (500 MHz, CDCl3): δ = 7.97 (d, J = 8.9 Hz, 1H), 7.27‒7.20 (m, 4H), 7.00 (s, 1H), 6.86 (dd, J = 8.9, 3.0 Hz, 1H), 6.77 (d, J = 3.0 Hz, 1H), 3.77 (s, 3H), 2.39 (s, 3H), 1.97 (s, 3H).

13C-NMR (126 MHz, CDCl₃): δ = 168.3 (Cq), 156.3 (C_q), 137.7 (C_q), 135.2 (C_q), 134.6 (C_q), 129.6 (CH), 128.8 (CH), 127.8 (C_q), 124.1 (CH), 115.4 (CH), 113.1 (CH), 55.4 (CH₃), 24.1 (CH₃), 21.1 (CH₃).

IR (ATR): 3269, 3022, 2971, 2921, 1660, 1520, 1267, 1176, 1031, 801 cm^‒1. MS (EI) m/z (relative intensity): 255 ([M⁺] 86), 213 (89), 198 (100), 43 (19).

HR-MS (EI) m/z for C16H17NO2 [M⁺] calcd.: 255.1259.

found: 255.1263.

Synthesis of Methyl (E)-2'-(phenyldiazenyl)-[1,1'-biphenyl]-4-carboxylate (83ba)

The general procedure D was followed using 13b (182 mg, 1.00 mmol) and methyl 4-bromobenzoate (52a) (108 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH₂Cl₂: 7/3) yielded 83ba (93 mg, 59%) as an orange solid.

M. p.: 128–129 °C.

1H-NMR (CDCl3, 500 MHz): δ = 8.09 (d, J = 8.6 Hz, 2H), 7.80‒7.72 (m, 3H), 7.57‒7.52 (m, 4H), 7.51‒7.42 (m, 4H), 3.94 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 167.2 (Cq), 152.7 (Cq), 149.6 (Cq), 143.7 (Cq), 140.2 (Cq), 131.1 (CH), 130.9 (CH), 130.9 (CH), 130.7 (CH), 129.1 (CH), 128.9 (CH), 128.8 (Cq), 128.7 (CH), 123.3 (CH), 116.0 (CH), 52.1 (CH3).

IR (ATR): 3071, 2947, 2920, 2848, 1721, 1437, 1273, 1103, 774, 736, 686, 541 cm^‒1.

MS (EI) m/z (relative intensity): 316 ([M⁺] 58), 301 (100), 257 (40), 211 (44), 152 (91), 77 (94).

HR-MS (EI) m/z for C₂₀H₁₆N₂O₂ [M⁺] calcd.: 316.1212.

found: 316.1205.

Synthesis of (E)-1-([1,1'-Biphenyl]-2-yl)-2-phenyldiazene (83bb)

The general procedure D was followed using 13b (182 mg, 1.00 mmol) and bromobenzene (52b) (79 mg, 0.50 mmol). Purification by column chromatography (n-hexane/EtOAc/NEt3: 88/6/6) yielded 83bb (68 mg, 53%) as an orange viscous oil.

1H-NMR (CDCl3, 300 MHz): δ = 7.81‒7.75 (m, 2H), 7.62‒7.35 (m, 12H).

13C-NMR (CDCl₃, 126 MHz): δ = 152.9 (C_q), 149.8 (C_q), 141.2 (C_q), 138.9 (C_q), 131.1 (CH), 131.0 (CH), 130.9 (CH), 130.8 (CH), 129.1 (CH), 128.1 (CH), 127.7 (CH), 127.3 (CH), 123.3 (CH), 116.0 (CH).

IR (ATR): 3058, 3030, 1470, 1149, 1008, 770, 730, 685, 535, 497 cm^‒1. MS (EI) m/z (relative intensity): 258 ([M⁺] 42), 152 (82), 84 (100), 77 (70).

HR-MS (EI) m/z for C₁₈H₁₄N₂ [M⁺] calcd.: 258.1157.

found: 258.1152.

Synthesis of Methyl (E)-3'-methyl-2'-(o-tolyldiazenyl)-[1,1'-biphenyl]-4-carboxylate (83ca)

The general procedure D was followed using 13c (210 mg, 1.00 mmol) and methyl 4-bromobenzoate (52a) (108 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH2Cl2: 7/3) yielded 83ca (103 mg, 60%) as an orange solid.

M. p.: 123‒124 °C.

1H-NMR (CDCl3, 500 MHz): δ = 7.97 (d, J = 8.1 Hz, 2H), 7.38‒7.26 (m, 9H), 3.92 (s, 3H), 2.47 (s, 3H), 2.28 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 167.1 (Cq), 150.9 (Cq), 150.7 (Cq), 145.4 (Cq), 138.5 (Cq), 134.7 (Cq), 131.3 (CH), 131.2 (CH), 131.1 (CH), 130.8 (Cq), 130.1 (CH), 129.1 (CH), 128.9 (CH), 128.1 (CH), 128.0 (C_q), 126.3 (CH), 115.0 (CH), 52.0 (CH₃), 19.2 (CH₃), 17.1 (CH₃).

IR (ATR): 3059, 2951, 2923, 2844, 1719, 1608, 1398, 1272, 1179, 1101, 856, 766, 739, 712 cm^‒1.

MS (EI) m/z (relative intensity): 344 ([M⁺] 60), 329 (93), 285 (30), 225 (50), 165 (99), 91 (100), 65 (34).

HR-MS (EI) m/z for C22H20N2O2 [M⁺] calcd.: 344.1525.

found: 344.1526.

Synthesis of (E)-1-{3'-Methyl-2'-(o-tolyldiazenyl)-[1,1'-biphenyl]-4-yl}ethan-1-one (83cc)

The general procedure D was followed using 13c (210 mg, 1.00 mmol) and 1-(4-bromophenyl)ethan-1-one (52c) (100 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH2Cl2: 7/3) yielded 83cc (87 mg, 53%) as an orange solid.

M. p.: 125‒126 °C.

1H-NMR (CDCl₃, 300 MHz): δ = 7.89 (d, J = 8.6 Hz, 2H), 7.37–7.29 (m, 6H), 7.26 (d, J = 0.8 Hz, 2H), 7.24–7.15 (m, 1H), 2.59 (s, 3H), 2.46 (s, 3H), 2.27 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 198.0 (Cq), 151.0 (C_q), 150.8 (C_q), 145.7 (C_q), 138.5 (C_q), 135.2 (C_q), 134.7 (C_q), 131.5 (CH), 131.4 (CH), 131.3 (CH), 130.9 (C_q), 130.4 (CH), 128.9 (CH), 128.2 (CH), 128.0 (CH), 126.4 (CH), 115.0 (CH), 26.5 (CH₃), 19.1 (CH₃), 17.0 (CH₃).

IR (ATR): 3054, 2961, 2923, 1679, 1603, 1356, 1264, 955, 766, 600 cm^‒1.

MS (EI) m/z (relative intensity): 328 ([M⁺] 100), 285 (32), 209 (25), 165 (45), 91 (98), 65 (27), 43 (90).

HR-MS (EI) m/z for C22H20N2O [M⁺] calcd.: 328.1576.

found: 328.1569.

Synthesis of Methyl (E)-5'-methyl-2'-(p-tolyldiazenyl)-[1,1'-biphenyl]-4-carboxylate (83da)

The general procedure D was followed using 13d (210 mg, 1.00 mmol) and methyl 4-bromobenzoate (52a) (108 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH2Cl2: 7/3) yielded 83da (112 mg, 65%) as an orange solid.

M. p.: 138‒139 °C.

1H-NMR (CDCl3, 500 MHz): δ = 8.08 (d, J = 8.6 Hz, 2H), 7.71 (d, J = 8.2 Hz, 1H), 7.64 (d, J = 8.2 Hz, 2H), 7.54 (d, J = 8.6 Hz, 2H), 7.37‒7.35 (m, 1H), 7.27 (ddq, J = 8.2, 2.0, 0.6 Hz, 1H), 7.25‒7.21 (m, 2H), 3.94 (s, 3H), 2.46 (s, 3H), 2.39 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 167.2 (C_q), 151.0 (C_q), 147.6 (C_q), 143.9 (C_q), 141.4 (C_q), 141.1 (C_q), 140.0 (C_q), 131.1 (CH), 130.8 (CH), 129.7 (CH), 129.5 (CH), 128.7 (CH), 128.6 (C_q), 123.1 (CH), 115.8 (CH), 52.1 (CH₃), 21.5 (CH₃), 21.5 (CH₃).

IR (ATR): 3029, 2948, 2921, 2844, 1721, 1599, 1437, 1274, 1149, 1112, 824, 702, 565, 385 cm^‒1.

MS (EI) m/z (relative intensity): 344 ([M⁺] 66), 329 (73), 285 (29), 225 (47), 165 (86), 91 (100), 65 (25).

HR-MS (ESI) m/z for C22H21N2O2 [M+H⁺] calcd.: 345.1603.

found: 345.1599.

Synthesis of Methyl (E)-4'-methyl-2'-(m-tolyldiazenyl)-[1,1'-biphenyl]-4-carboxylate (83aa)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and methyl 4-bromobenzoate (52a) (108 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH2Cl2: 7/3) yielded 83aa (150 mg, 87%) as an orange solid.

M. p.: 136‒137 °C.

1H-NMR (CDCl₃, 300 MHz): δ = 8.10 (d, J = 8.0 Hz, 2H), 7.64 (s, 1H), 7.60‒7.53 (m, 4H), 7.49 (d, J = 7.8 Hz, 1H), 7.40‒7.32 (m, 2H), 7.30‒7.24 (m, 1H), 3.96 (s, 3H), 2.48 (s, 3H), 2.42 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 167.0 (C_q), 152.7 (C_q), 149.3 (C_q), 143.6 (C_q), 138.8 (C_q), 138.7 (C_q), 137.1 (C_q), 131.7 (CH), 131.5 (CH), 130.7 (CH), 130.4 (CH), 128.8 (CH), 128.7 (CH), 128.5 (C_q), 124.2 (CH), 119.8 (CH), 116.1 (CH), 52.1 (CH₃), 21.4 (CH₃), 21.3 (CH₃).

IR (ATR): 3030, 2951, 2914, 2850, 1721, 1606, 1438, 1279, 1106, 829, 790 cm^‒1.

MS (EI) m/z (relative intensity): 344 ([M⁺] 60), 329 (80), 285 (38), 225 (43), 165 (87), 91 (100), 65 (25), 43 (22).

HR-MS (EI) m/z for C22H20N2O2 [M⁺] calcd.: 344.1525.

found: 344.1511.

Synthesis of Methyl (E)-4'-ethyl-2'-{(3-ethylphenyl)diazenyl}-[1,1'-biphenyl]-4-carboxylate (83ea)

The general procedure D was followed using 13e (238 mg, 1.00 mmol) and methyl 4-bromobenzoate (52a) (108 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH2Cl2: 7/3) yielded 83ea (155 mg, 83%) as an orange solid.

M. p.: 81‒82 °C.

1H-NMR (CDCl₃, 500 MHz): δ = 8.07 (d, J = 8.6 Hz, 2H), 7.68‒7.65 (m, 1H), 7.61‒7.59 (m, 1H), 7.57‒7.52 (m, 3H), 7.50 (dd, J = 7.9, 0.5 Hz, 1H), 7.39 (dd, J = 7.9, 1.8 Hz, 1H), 7.35 (t, J = 7.7 Hz, 1H), 7.29‒7.26 (m, 1H), 3.94 (s, 3H), 2.77 (q, J = 7.6 Hz, 2H), 2.71 (q, J = 7.6 Hz, 2H), 1.32 (t, J = 7.6 Hz, 3H), 1.26 (t, J = 7.6 Hz, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 167.2 (Cq), 153.0 (Cq), 149.6 (Cq), 145.3 (Cq), 145.2 (Cq), 143.8 (C_q), 137.5 (C_q), 130.9 (CH), 130.7 (CH), 130.6 (CH), 130.5 (CH), 129.0 (CH), 128.8 (CH), 128.6 (Cq), 123.4 (CH), 119.8 (CH), 115.0 (CH), 52.1 (CH3), 28.7 (CH2), 28.7 (CH2), 15.4 (CH3), 15.3 (CH3).

IR (ATR): 2962, 2930, 2871, 1717, 1606, 1439, 1273, 1181, 1102, 691 cm^‒1.

MS (EI) m/z (relative intensity): 372 ([M⁺] 89), 357 (100), 313 (45), 239 (61), 180 (35), 165 (75), 105 (91), 77 (32).

HR-MS (ESI) m/z for C24H25N2O2 [M+H⁺] calcd.: 373.1916.

found: 373.1915.

Synthesis of Methyl (E)-4'-isopropyl-2'-{(3-isopropylphenyl)diazenyl}-[1,1'-biphenyl]-4-carboxylate (83fa)

The general procedure D was followed using 13f (266 mg, 1.00 mmol) and methyl 4-bromobenzoate (52a) (108 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH2Cl2: 7/3) yielded 83fa (160 mg, 80%) as an orange solid.

M. p.: 92‒93 °C.

1H-NMR (CDCl3, 500 MHz): δ = 8.07 (d, J = 8.5 Hz, 2H), 7.71 (t, J = 1.8 Hz, 1H), 7.63 (d, J = 1.9 Hz, 1H), 7.56‒7.50 (m, 4H), 7.43 (dd, J = 8.0, 1.9 Hz, 1H), 7.35 (t, J = 7.7 Hz, 1H), 7.32‒7.29 (m, 1H), 3.93 (s, 3H), 3.04 (sept, J = 6.9 Hz, 1H), 2.97 (sep, J = 6.9 Hz, 1H), 1.33 (d, J = 6.9 Hz, 6H), 1.27 (d, J = 6.9 Hz, 6H).

13C-NMR (CDCl₃, 126 MHz): δ = 167.2 (Cq), 153.1 (C_q), 150.0 (C_q), 149.9 (C_q), 149.5 (C_q), 143.8 (C_q), 137.7 (C_q), 130.9 (CH), 130.6 (CH), 129.4 (CH), 129.1 (CH), 129.0 (CH), 128.8 (CH), 128.6 (C_q), 122.4 (CH), 119.6 (CH), 113.7 (CH), 52.1 (CH₃), 34.1 (CH), 34.0 (CH), 23.9 (CH₃), 23.8 (CH₃).

IR (ATR): 2959, 2889, 2868, 1718, 1607, 1439, 1273, 1113, 858, 835, 797, 694 cm^‒1.

MS (EI) m/z (relative intensity): 400 ([M⁺] 96), 385 (100), 341 (41), 253 (45), 211 (47), 179 (43), 119 (78), 91 (42).

HR-MS (EI) m/z for C26H28N2O2 [M⁺] calcd.: 400.2151.

found: 400.2138.

Synthesis of Methyl (E)-4'-methoxy-2'-{(3-methoxyphenyl)diazenyl}-[1,1'-biphenyl]-4-carboxylate (83ga)

The general procedure D was followed using 13g (242 mg, 1.00 mmol) and methyl 4-bromobenzoate (52a) (108 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH₂Cl₂: 7/3) yielded 83ga (139 mg, 74%) as an orange solid.

M. p.: 145‒146 °C.

1H-NMR (CDCl₃, 500 MHz): δ = 8.06 (d, J = 8.6 Hz, 2H), 7.53‒7.48 (m, 3H), 7.44 (ddd, J = 7.8, 1.7, 1.0 Hz, 1H), 7.37 (d, J = 8.1 Hz, 1H), 7.35‒7.33 (m, 1H), 7.27 (dd, J = 2.6, 1.7 Hz, 1H), 7.13 (dd, J = 8.5, 2.7 Hz, 1H), 7.02‒6.98 (m, 1H), 3.93 (s, 3H), 3.91 (s, 3H), 3.78 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 167.1 (Cq), 160.3 (Cq), 160.0 (Cq), 153.9 (Cq), 150.0 (Cq), 143.5 (Cq), 133.5 (Cq), 131.6 (CH), 130.9 (CH), 129.8 (CH), 128.7 (CH), 128.4 (Cq), 118.4 (CH), 118.0 (CH), 117.4 (CH), 106.2 (CH), 99.3 (CH), 55.6 (CH3), 55.3 (CH3), 52.1 (CH3).

IR (ATR): 2950, 2902, 2834, 1719, 1597, 1519, 1481, 1433, 1270, 1132, 1103, 1039, 887, 782, 683 cm^‒1.

MS (EI) m/z (relative intensity): 376 ([M⁺] 64), 361 (100), 317 (53), 241 (38), 182 (35), 139 (54), 107 (65), 77 (38).

HR-MS (ESI) m/z for C₂₂H₂₁N₂O₄ [M+H⁺] calcd.: 377.1501.

found: 377.1491.

Synthesis of (E)-1-{4'-Methoxy-2'-[(3-methoxyphenyl)diazenyl]-[1,1'-biphenyl]-4-yl}ethan-1-one (83gc)

The general procedure D was followed using 13g (242 mg, 1.00 mmol) and methyl 4-bromobenzoate (52c) (100 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH₂Cl₂: 7/3) yielded 83gc (96 mg, 53%) as an orange solid.

M. p.: 155‒156 °C.

1H-NMR (CDCl3, 300 MHz): δ = 7.98 (d, J = 8.5 Hz, 2H), 7.56–7.47 (m, 3H), 7.44 (ddd, J = 7.8, 1.4, 1.3 Hz, 1H), 7.38 (d, J = 8.0 Hz, 1H), 7.34 (d, J = 2.8 Hz, 1H), 7.29–7.23 (m, 1H), 7.13 (dd, J = 8.6, 2.7 Hz, 1H), 7.00 (ddd, J = 8.0, 2.7, 1.2 Hz, 1H), 3.91 (s, 3H), 3.78 (s, 3H), 2.63 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 198.1 (Cq), 160.4 (Cq), 160.2 (Cq), 154.0 (Cq), 150.2 (Cq), 143.8 (Cq), 135.4 (Cq), 133.4 (Cq), 131.6 (CH), 131.1 (CH), 129.9 (CH), 127.6 (CH), 118.5 (CH), 118.0 (CH), 117.4 (CH), 106.4 (CH), 99.4 (CH), 55.6 (CH₃), 55.3 (CH₃), 26.6 (CH₃).

IR (ATR): 3068, 3005, 2961, 2940, 2915, 2834, 1673, 1604, 1513, 1269, 1132, 1040, 887, 819, 782, 634 cm^‒1.

MS (EI) m/z (relative intensity): 360 ([M⁺] 100), 317 (57), 139 (38), 107 (53), 92 (24), 77 (30), 43 (54).

HR-MS (EI) m/z for C₂₂H₂₀N₂O₃ [M⁺] calcd.: 360.1474.

found: 360.1466.

Synthesis of (E)-1-(4'-Chloro-4-methyl-[1,1'-biphenyl]-2-yl)-2-(m-tolyl)diazene (83ad)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 1-bromo-4-chlorobenzene (52d) (96 mg, 0.50 mmol). Purification by column chromatography (n-hexane/EtOAc/NEt₃: 88/6/6) yielded 83ad (93 mg, 58%) as an orange solid.

M. p.: 120‒121 °C.

1H-NMR (CDCl3, 500 MHz): δ = 7.73‒7.69 (m, 1H), 7.60 (s, 1H), 7.56 (d, J = 7.9 Hz, 1H), 7.53 (s, 1H), 7.42 (d, J = 7.9 Hz, 1H), 7.38‒7.36 (m, 3H), 7.36‒7.32 (m, 2H), 7.29‒7.25 (m, 1H), 2.45 (s, 3H), 2.41 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 152.9 (Cq), 149.5 (Cq), 139.0 (Cq), 138.5 (Cq), 137.3 (Cq), 137.1 (Cq), 133.2 (Cq), 132.1 (CH), 131.8 (CH), 131.7 (CH), 130.4 (CH), 128.9 (CH), 127.7 (CH), 124.2 (CH), 120.0 (CH), 116.2 (CH), 21.4 (CH3), 21.2 (CH3).

IR (ATR): 3049, 3028, 2949, 2920, 2859, 1596, 1479, 1092, 1005, 811, 788, 747, 687 cm^‒1. MS (EI) m/z (relative intensity): 320 ([M⁺] 67), 201 (54), 166 (93), 91 (100), 65 (35).

HR-MS (ESI) m/z for C₂₀H₁₈ClN₂ [M+H⁺] calcd.: 321.1159.

found: 321.1141.

Synthesis of (E)-N,N,4'-Trimethyl-2'-(m-tolyldiazenyl)-[1,1'-biphenyl]-4-amine (83ae)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 4-bromo-N,N-dimethylaniline (52e) (100 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH₂Cl₂: 7/3) yielded 83ae (92 mg, 56%) as an orange solid.

M. p.: 124‒125 °C.

1H-NMR (CDCl₃, 500 MHz): δ = 7.68 (s, 1H), 7.65 (d, J = 7.3 Hz, 1H), 7.49 (d, J = 7.9 Hz, 2H), 7.38–7.34 (m, 3H), 7.33–7.31 (m, 1H), 7.25 (d, J = 6.8 Hz, 1H), 6.80 (d, J = 8.7 Hz, 2H), 3.00 (s, 6H), 2.44 (s, 3H), 2.42 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 153.1 (Cq), 149.7 (Cq), 149.6 (Cq), 138.8 (Cq), 138.2 (Cq), 136.7 (Cq), 131.8 (CH), 131.5 (CH), 131.3 (CH), 130.3 (CH), 128.8 (CH), 126.7 (Cq), 124.0 (CH), 120.2 (CH), 116.2 (CH), 111.8 (CH), 40.6 (CH3), 21.4 (CH3), 21.1 (CH3).

IR (ATR): 2915, 2858, 2803, 1611, 1528, 1494, 1444, 1353, 1196, 806, 686, 532 cm^‒1. MS (EI) m/z (relative intensity): 329 ([M⁺] 100), 285 (12), 210 (29), 167 (19), 91 (19), 65 (8).

HR-MS (EI) m/z for C22H23N3 [M⁺] calcd.: 329.1892.

found: 329.1874.

Synthesis of (E)-1-(4'-Methoxy-4-methyl-[1,1'-biphenyl]-2-yl)-2-(m-tolyl)diazene (83af)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 1-bromo-4-methoxybenzene (52f) (94 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH₂Cl₂: 7/3) yielded 83af (106 mg, 67%) as an orange solid.

M. p.: 121‒122 °C.

1H-NMR (CDCl₃, 300 MHz): δ = 7.66 (s, 1H), 7.62 (d, J = 7.8 Hz, 1H), 7.53 (s, 1H), 7.47 (d, J = 7.8 Hz, 1H), 7.43–7.38 (m, 2H), 7.37–7.31 (m, 2H), 7.29‒7.23 (m, 1H), 6.97 (d, J = 8.9 Hz, 2H), 3.87 (s, 3H), 2.46 (s, 3H), 2.43 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 158.8 (Cq), 152.9 (Cq), 149.4 (Cq), 138.8 (Cq), 137.7 (Cq), 137.3 (Cq), 131.9 (CH), 131.5 (CH), 131.4 (CH), 131.1 (Cq), 130.4 (CH), 128.7 (CH), 124.0 (CH), 120.0 (CH), 116.0 (CH), 113.0 (CH), 55.3 (CH3), 21.4 (CH3), 21.2 (CH3).

IR (ATR): 2962, 2914, 2856, 1606, 1518, 1249, 1177, 1016, 816, 791, 689, 538 cm^‒1.

MS (EI) m/z (relative intensity): 316 ([M⁺] 100), 301 (40), 197 (67), 182 (65), 153 (42), 91 (78), 65 (30).

HR-MS (EI) m/z for C21H20N2O [M⁺] calcd.: 316.1576.

found: 316.1577.

Synthesis of (E)-4'-Methyl-2'-(m-tolyldiazenyl)-[1,1'-biphenyl]-4-carbaldehyde (83ag)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 4-bromobenzaldehyde (52g) (93 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH₂Cl₂: 7/3) yielded 83ag (80 mg, 51%) as an orange solid.

M. p.: 101‒102 °C.

1H-NMR (CDCl3, 500 MHz): δ = 10.07 (s, 1H), 7.91 (d, J = 8.4 Hz, 2H), 7.62 (d, J = 8.1 Hz, 2H), 7.59 (s, 1H), 7.57 (s, 1H), 7.54 (d, J = 7.3 Hz, 1H), 7.47 (d, J = 7.8 Hz, 1H), 7.38 (ddd, J = 7.8, 1.8, 0.8 Hz, 1H), 7.33 (t, J = 7.7 Hz, 1H), 7.25 (d, J = 9.7 Hz, 1H), 2.47 (s, 3H), 2.40 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 192.2 (Cq), 152.8 (Cq), 149.5 (Cq), 145.4 (Cq), 139.3 (Cq), 139.0 (Cq), 137.0 (Cq), 134.9 (Cq), 131.9 (CH), 131.7 (CH), 131.5 (CH), 130.5 (CH), 128.9 (CH), 128.9 (CH), 124.3 (CH), 119.9 (CH), 116.3 (CH), 21.4 (CH3), 21.3 (CH3).

IR (ATR): 2915, 2816, 2727, 1694, 1603, 1210, 818, 792, 686, 537 cm^‒1.

MS (EI) m/z (relative intensity): 314 ([M⁺] 79), 195 (32), 165 (60), 152 (47), 91 (100), 65 (31), 43 (33).

HR-MS (EI) m/z for C₂₁H₁₈N₂O [M⁺] calcd.: 314.1419.

found: 314.1430.

Synthesis of (E)-1-{4'-Methyl-2'-(m-tolyldiazenyl)-[1,1'-biphenyl]-4-yl}ethan-1-one (83ac)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 1-(4-bromophenyl)ethan-1-one (52c) (100 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH2Cl2: 7/3) yielded 83ac (106 mg, 65%) as an orange solid.

M. p.: 123‒124 °C.

1H-NMR (CDCl₃, 300 MHz): δ = 8.00 (d, J = 8.6 Hz, 2H), 7.61 (s, 1H), 7.59–7.51 (m, 4H), 7.46 (d, J = 7.8 Hz, 1H), 7.39‒7.29 (m, 2H), 7.28‒7.21 (m, 1H), 2.64 (s, 3H), 2.47 (s, 3H), 2.40 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 198.1 (Cq), 152.9 (C_q), 149.6 (C_q), 144.0 (C_q), 139.0 (C_q), 138.9 (C_q), 137.2 (C_q), 135.6 (C_q), 131.9 (CH), 131.7 (CH), 131.0 (CH), 130.5 (CH), 129.0 (CH), 127.6 (CH), 124.4 (CH), 119.9 (CH), 116.3 (CH), 26.5 (CH3), 21.2 (CH3), 21.1 (CH3).

IR (ATR): 2914, 2856, 2723, 1679, 1600, 1266, 819, 797, 688, 599 cm^‒1.

MS (EI) m/z (relative intensity): 328 ([M⁺] 100), 285 (44), 209 (25), 165 (41), 91 (83), 65 (19), 65 (20), 43 (76).

HR-MS (EI) m/z for C22H20N2O [M⁺] calcd.: 328.1576.

found: 328.1572.

Synthesis of Ethyl (E)-4'-methyl-2'-(m-tolyldiazenyl)-[1,1'-biphenyl]-4-carboxylate (83ah)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and ethyl 4-bromobenzoate (52h) (115 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH₂Cl₂: 7/3) yielded 83ah (113 mg, 63%) as an orange solid.

M. p.: 94‒95 °C.

1H-NMR (CDCl₃, 300 MHz): δ = 8.09 (d, J = 8.5 Hz, 2H), 7.63‒7.60 (m, 1H), 7.58‒7.50 (m, 4H), 7.47 (d, J = 7.9 Hz, 1H), 7.39‒7.30 (m, 2H), 7.28‒7.22 (m, 1H), 4.41 (q, J = 7.1 Hz, 2H), 2.47 (s, 3H), 2.41 (s, 3H), 1.41 (t, J = 7.1 Hz, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 166.8 (Cq), 153.0 (Cq), 149.6 (Cq), 143.7 (Cq), 139.0 (Cq), 138.9 (Cq), 137.4 (Cq), 131.9 (CH), 131.7 (CH), 130.8 (CH), 130.6 (CH), 129.0 (Cq), 128.9 (CH), 128.8 (CH), 124.4 (CH), 119.9 (CH), 116.3 (CH), 60.9 (CH2), 21.3 (CH3), 21.1 (CH3), 14.3 (CH3).

IR (ATR): 2979, 2921, 2867, 1713, 1607, 1268, 1180, 1100, 775, 688 cm^‒1.

MS (EI) m/z (relative intensity): 358 ([M⁺] 47), 329 (100), 285 (37), 239 (19), 211 (17), 165 (60), 91 (80), 65 (14).

HR-MS (EI) m/z for C23H22N2O2 [M⁺] calcd.: 358.1681.

found: 358.1669.

Synthesis of (E)-4'-Methyl-2'-(m-tolyldiazenyl)-[1,1'-biphenyl]-4-carbonitrile (83ai)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 4-bromobenzonitrile (52i) (91 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH₂Cl₂: 7/3) yielded 83ai (100 mg, 64%) as an orange solid.

M. p.: 121‒122 °C.

1H-NMR (CDCl₃, 500 MHz): δ = 7.58 (d, J = 8.6 Hz, 2H), 7.59–7.56 (m, 2H), 7.55 (d, J = 8.6 Hz, 2H), 7.53–7.51 (m, 1H), 7.43 (d, J = 7.9 Hz, 1H), 7.39–7.33 (m, 2H), 7.27 (d, J = 8.0 Hz, 1H), 2.47 (s, 3H), 2.41 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 152.8 (Cq), 149.3 (Cq), 143.8 (Cq), 139.5 (Cq), 139.1 (Cq), 136.5 (Cq), 132.0 (CH), 131.8 (CH), 131.4 (CH), 131.2 (CH), 130.3 (CH), 129.0 (CH), 124.1 (CH), 120.0 (CH), 119.1 (Cq), 116.3 (CH), 110.7 (Cq), 21.3 (CH3), 21.3 (CH3).

IR (ATR): 2968, 2919, 2857, 2225, 1603, 1484, 812, 787, 682, 589, 544 cm^‒1.

MS (EI) m/z (relative intensity): 311 ([M⁺] 58), 192 (56), 165 (32), 119 (18), 91 (100), 65 (27).

HR-MS (EI) m/z for C₂₁H₁₇N₃ [M⁺] calcd.: 311.1422.

found: 311.1419.

Synthesis of (E)-1-(4-Methyl-4'-nitro-[1,1'-biphenyl]-2-yl)-2-(m-tolyl)diazene (83aj)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 1-bromo-4-nitrobenzene (52j) (101 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH₂Cl₂: 7/3) yielded 83aj (89 mg, 54%) as an orange solid.

M. p.: 134‒135 °C.

1H-NMR (CDCl₃, 500 MHz): δ = 8.25 (d, J = 8.9 Hz, 2H), 7.63–7.57 (m, 4H), 7.53 (d, J = 7.9 Hz, 1H), 7.45 (d, J = 7.8 Hz, 1H), 7.38 (ddd, J = 7.9, 1.8, 0.6 Hz, 1H), 7.35 (t, J = 7.7 Hz, 1H), 7.27 (d, J = 7.5 Hz, 1H), 2.48 (s, 3H), 2.41 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 152.8 (Cq), 149.3 (Cq), 146.9 (Cq), 145.9 (Cq), 139.8 (Cq), 139.1 (Cq), 136.1 (Cq), 132.1 (CH), 131.8 (CH), 131.5 (CH), 130.4 (CH), 129.0 (CH), 124.3 (CH), 122.7 (CH), 119.9 (CH), 116.4 (CH), 21.4 (CH3), 21.3 (CH3).

IR (ATR): 2915, 2856, 1596, 1506, 1345, 853, 810, 786, 733, 695, 685 cm^‒1.

MS (EI) m/z (relative intensity): 331 ([M⁺] 39), 212 (32), 165 (56), 119 (22), 91 (100), 65 (24).

HR-MS (EI) m/z for C20H17N3O2 [M⁺] calcd.: 331.1321.

found: 331.1319.

Synthesis of (E)-1-(3'-Methoxy-4-methyl-[1,1'-biphenyl]-2-yl)-2-(m-tolyl)diazene (83ak)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 1-bromo-3-methoxybenzene (52k) (94 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH2Cl2: 7/3) yielded 83ak (89 mg, 56%) a viscous orange liquid.

1H-NMR (CDCl3, 500 MHz): δ = 7.65 (m, 2H), 7.57–7.54 (m, 1H), 7.51 (ddd, J = 7.8, 4.0, 1.4 Hz, 1H), 7.40–7.31 (m, 3H), 7.26 (d, J = 7.4 Hz, 1H), 7.09–7.03 (m, 2H), 6.97–6.92 (m, 1H), 3.81 (s, 3H), 2.48 (s, 3H), 2.42 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 158.9 (Cq), 153.0 (Cq), 149.6 (Cq), 140.2 (Cq), 138.9 (Cq), 138.1 (Cq), 138.0 (Cq), 131.6 (CH), 131.5 (CH), 130.6 (CH), 128.8 (CH), 128.4 (CH), 123.8 (CH), 123.5 (CH), 120.3 (CH), 116.3 (CH), 116.1 (CH), 113.0 (CH), 55.2 (CH3), 21.3 (CH3), 21.2 (CH3).

IR (ATR): 3024, 2918, 2832, 1599, 1477, 1283, 1208, 1023, 821, 786, 746, 688 cm^‒1.

MS (EI) m/z (relative intensity): 316 ([M⁺] 100), 285 (52), 197 (55), 182 (69), 153 (40), 91 (86), 65 (34).

HR-MS (EI) m/z for C₂₁H₂₀N₂O [M⁺] calcd.: 316.1576.

found: 316.1571.

Synthesis of (E)-1-(m-Tolyl)-2-(3',4',5'-trimethoxy-4-methyl-[1,1'-biphenyl]-2-yl)diazene (83al)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 5-bromo-1,2,3-trimethoxybenzene (52l) (124 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH2Cl2: 7/3) yielded 83al (161 mg, 86%) as an orange solid.

M. p.: 138‒139 °C.

1H-NMR (CDCl₃, 500 MHz): δ = 7.64 (m, 2H), 7.54–7.48 (m, 2H), 7.38–7.32 (m, 2H), 7.25 (d, J = 7.7 Hz, 1H), 6.68 (s, 2H) 3.91 (s, 3H), 3.81 (s, 6H), 2.45 (s, 3H), 2.39 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 152.9 (Cq), 152.4 (Cq), 149.7 (Cq), 138.9 (Cq), 138.1 (Cq), 137.8 (Cq), 137.3 (Cq), 134.3 (Cq), 131.7 (CH), 131.5 (CH), 130.3 (CH), 128.9 (CH), 123.5 (CH), 120.5 (CH), 116.3 (CH), 108.3 (CH), 60.9 (CH3), 56.0 (CH3), 21.3 (CH3), 21.1 (CH3).

IR (ATR): 2948, 2921, 2825, 1584, 1449, 1412, 1235, 1120, 1011, 817, 790, 686 cm^‒1. MS (EI) m/z (relative intensity): 376 ([M⁺] 45), 345 (100), 226 (33), 211 (30), 91 (37).

HR-MS (EI) m/z for C23H24N2O3 [M⁺] calcd.: 376.1787.

found: 376.1787.

Synthesis of (E)-1-(3',4'-Dichloro-4-methyl-[1,1'-biphenyl]-2-yl)-2-(m-tolyl)diazene (83am)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 4-bromo-1,2-dichlorobenzene (52m) (113 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH2Cl2: 7/3) yielded 83am (112 mg, 63%) as an orange solid.

M. p.: 127‒128 °C.

1H-NMR (CDCl₃, 500 MHz): δ = 7.62‒7.56 (m, 4H), 7.46 (d, J = 8.3 Hz, 1H), 7.42 (d, J = 7.8 Hz, 1H), 7.38‒7.33 (m, 2H), 7.29‒7.25 (m, 2H), 2.46 (s, 3H), 2.42 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 152.9 (Cq), 149.1 (Cq), 139.1 (Cq), 139.0 (Cq), 138.8 (Cq), 136.0 (Cq), 132.6 (CH), 131.9 (CH), 131.8 (CH), 131.7 (Cq), 131.3 (Cq), 130.2 (CH), 130.1 (CH), 129.4 (CH), 129.0 (CH), 123.7 (CH), 120.5 (CH), 116.2 (CH), 21.4 (CH3), 21.2 (CH3).

IR (ATR): 3026, 2918, 2858, 1601, 1463, 1371, 1133, 1027, 882, 826, 808, 686 cm^‒1.

MS (EI) m/z (relative intensity): 354 ([M⁺] 55), 235 (43), 200 (62), 165 (61), 91 (100), 65 (36).

HR-MS (EI) m/z for C20H16Cl2N2 [M⁺] calcd.: 354.0691.

found: 354.0686.

Synthesis of (E)-1-{5-Methyl-2-(thiophen-2-yl)phenyl}-2-(m-tolyl)diazene (83an)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 2-bromothiophene (52n) (82 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH₂Cl₂: 7/3) yielded 83an (91 mg, 62%) as a viscous orange liquid.

1H-NMR (CDCl₃, 400 MHz): δ = 7.83 (d, J = 8.7 Hz, 1H), 7.74 (m, 2H), 7.55–7.29 (m, 6H), 7.14 (dd, J = 5.2, 3.8 Hz, 1H), 2.48 (s, 3H), 2.45 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 152.8 (Cq), 148.3 (Cq), 139.8 (Cq), 138.9 (Cq), 137.9 (Cq), 131.8 (CH), 131.6 (CH), 130.9 (Cq), 128.8 (CH), 128.3 (CH), 126.8 (CH), 124.7 (CH), 122.8 (CH), 120.6 (CH), 120.4 (CH), 116.2 (CH), 21.3 (CH3), 21.1 (CH3).

IR (ATR): 3050, 2917, 2858, 1599, 1482, 1240, 1083, 814, 790, 695, 515, 446 cm^‒1.

MS (EI) m/z (relative intensity): 292 ([M⁺] 40), 259 (33), 173 (47), 129 (35), 91 (100), 65 (31).

HR-MS (EI) m/z for C18H16N2S [M⁺] calcd.: 292.1034.

found: 292.1023.

Synthesis of (E)-1-{5-Methyl-2-(thiophen-3-yl)phenyl}-2-(m-tolyl)diazene (83ao)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 3-bromothiophene (52o) (82 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH2Cl2: 7/3) yielded 83ao (75 mg, 51%) as a viscous orange liquid.

1H-NMR (CDCl₃, 400 MHz): δ = 7.67 (m, 2H), 7.55 (d, J = 7.9 Hz, 1H), 7.51–7.46 (m, 1H), 7.39 (d, J = 7.7 Hz, 1H), 7.36–7.33 (m, 3H), 7.31 (ddd, J = 7.9, 1.9, 0.7 Hz, 1H), 7.27 (d, J = 7.5 Hz, 1H), 2.45 (s, 3H), 2.43 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 153.0 (Cq), 149.6 (C_q), 139.0 (C_q), 139.0 (C_q), 137.8 (C_q), 132.6 (C_q), 131.7 (CH), 131.7 (CH), 129.9 (CH), 129.9 (CH), 128.9 (CH), 124.8 (CH), 124.3 (CH), 124.1 (CH), 120.3 (CH), 116.3 (CH), 21.4 (CH₃), 21.2 (CH₃).

IR (ATR): 3089, 3025, 2913, 2855, 1607, 1494, 1190, 1082, 861, 824, 783, 741 cm^‒1. MS (EI) m/z (relative intensity): 292 ([M⁺] 100), 173 (68), 129 (40), 91 (79), 65 (23).

HR-MS (EI) m/z for C18H16N2S [M⁺] calcd.: 292.1034.

found: 292.1024.

Synthesis of (E)-5-{4-Methyl-2-(m-tolyldiazenyl)phenyl}-1H-indole (83ap)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 5-bromo-1H-indole (52p) (98 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH2Cl2: 7/3) yielded 83ap (88 mg, 54%) as a yellow solid.

M. p.: 72‒73 °C.

1H-NMR (CDCl3, 500 MHz): δ = 8.17 (bs, 1H), 7.77–7.70 (m, 1H), 7.64–7.51 (m, 3H), 7.40 (ddd, J = 8.4, 0.8, 0.8 Hz, 1H), 7.35 (ddd, J = 7.8, 1.8, 0.6 Hz, 1H), 7.32–7.28 (m, 2H), 7.26–

7.18 (m, 4H), 2.46 (s, 3H), 2.36 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 153.1 (Cq), 149.8 (C_q), 139.3 (C_q), 138.8 (C_q), 137.1 (C_q), 135.1 (C_q), 131.5 (CH), 131.3 (CH), 131.1 (CH), 130.5 (C_q), 128.8 (CH), 127.7 (C_q), 125.8 (CH), 124.5 (CH), 123.9 (CH), 123.1 (CH), 120.3 (CH), 116.1 (CH), 109.9 (CH), 103.1 (CH), 21.3 (CH₃), 21.1 (CH₃).

IR (ATR): 3089, 3025, 2913, 2855, 1607, 1494, 1480, 1190, 1082, 861, 824, 783, 741, 684 cm^‒1.

MS (EI) m/z (relative intensity): 325 ([M⁺] 100), 219 (25), 204 (21), 191 (27), 179 (48), 91 (21).

HR-MS (EI) m/z for C22H19N3 [M⁺] calcd.: 325.1579.

found: 325.1580.

Synthesis of (E)-1-{2-(Benzo[d][1,3]dioxol-5-yl)-5-methylphenyl}-2-(m-tolyl)diazene (83aq)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 5-bromobenzo[d][1,3]dioxole (52q) (101 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH2Cl2: 7/3) yielded 83aq (122 mg, 74%) as an orange solid.

M. p.: 131‒132 °C.

1H-NMR (CDCl₃, 500 MHz): δ = 7.63 (d, J = 0.7 Hz, 1H), 7.61 (dd, J = 7.9, 0.7 Hz, 1H), 7.50 (d, J = 0.7 Hz, 1H), 7.43 (d, J = 7.9 Hz, 1H), 7.36 (dd, J = 7.8, 7.8 Hz, 1H), 7.32 (ddd, J = 7.8, 1.9, 0.7 Hz, 1H), 7.25 (ddd, J = 7.8, 1.9, 0.7 Hz, 1H), 6.99 (dd, J = 1.6, 0.7 Hz, 1H), 6.87 (d, J = 1.6 Hz, 1H), 6.86 (d, J = 0.7 Hz, 1H), 6.00 (s, 2H), 2.44 (s, 3H), 2.41 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 153.1 (Cq), 149.7 (C_q), 147.3 (C_q), 147.0 (C_q), 139.0 (C_q), 137.9 (Cq), 137.8 (Cq), 132.8 (Cq), 131.6 (CH), 131.5 (CH), 130.6 (CH), 128.9 (CH), 124.8 (CH), 124.0 (CH), 120.3 (CH), 116.3 (CH), 111.3 (CH), 107.6 (CH), 101.1 (CH2), 21.3 (CH3), 21.0 (CH3).

IR (ATR): 2914, 1475, 1338, 1217, 1035, 935, 801, 686, 637, 530 cm^‒1.

MS (EI) m/z (relative intensity): 330 ([M⁺] 60), 329 (100), 224 (29), 181 (29), 153 (53), 91 (44), 65 (16), 43 (15).

HR-MS (EI) m/z for C21H18N2O2 [M⁺] calcd.: 330.1368.

found: 330.1360.

Synthesis of (E)-3-{4-Methyl-2-(m-tolyldiazenyl)phenyl}pyridine (83ar)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 3-bromopyridine (52r) (79 mg, 0.50 mmol). Purification by column chromatography (n-hexane/EtOAc/NEt₃: 88/6/6) yielded 83ar (45 mg, 31%) as an orange solid.

M. p.: 107‒108 °C.

1H-NMR (CDCl3, 400 MHz): δ = 8.73 (dd, J = 2.4, 0.7 Hz, 1H), 8.58 (dd, J = 4.9, 1.7 Hz, 1H), 7.75 (ddd, J = 7.9, 2.4, 1.7 Hz, 1H), 7.61‒7.57 (m, 2H), 7.56 (dd, J = 7.8, 0.7 Hz, 1H), 7.45 (d, J = 7.8 Hz, 1H), 7.38 (ddd, J = 7.8, 1.8, 0.7 Hz, 1H), 7.35‒7.31 (m, 2H), 7.25 (ddd, J = 7.8, 1.8, 0.7 Hz, 1H), 2.47 (s, 3H), 2.39 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 152.8 (Cq), 151.0 (CH), 149.4 (Cq), 148.1 (CH), 139.1 (C_q), 139.0 (C_q), 137.9 (CH), 135.1 (C_q), 134.6 (C_q), 132.0 (CH), 131.9 (CH), 130.5 (CH), 128.9 (CH), 124.1 (CH), 122.5 (CH), 120.1 (CH), 116.3 (CH), 21.3 (CH₃), 21.2 (CH₃).

IR (ATR): 3023, 2917, 1412, 997, 829, 799, 709, 689, 626, 487 cm^‒1.

MS (EI) m/z (relative intensity): 287 ([M⁺] 63), 286 (81), 168 (76), 91 (100), 65 (35), 43 (58).

HR-MS (EI) m/z for C₁₉H₁₇N₃ [M⁺] calcd.: 287.1422.

found: 287.1409.

Synthesis of (E)-5-{4-Methyl-2-(m-tolyldiazenyl)phenyl}pyrimidine (83as)

The general procedure D was followed using 13a (210 mg, 1.00 mmol) and 5-bromopyrimidine (52s) (79 mg, 0.50 mmol). Purification by column chromatography (n-hexane/EtOAc/NEt3: 88/6/6) yielded 83as (40 mg, 28%) as an orange solid.

M. p.: 126‒127 °C.

1H-NMR (CDCl3, 400 MHz): δ = 9.18 (s, 1H), 8.85 (s, 2H), 7.67 (d, J = 0.7 Hz, 1H), 7.59 (d, J = 0.7 Hz, 1H), 7.56 (ddd, J = 7.7, 1.9, 0.7 Hz, 1H), 7.45 (d, J = 7.8 Hz, 1H), 7.42 (dd, J = 7.8, 0.7 Hz, 1H), 7.34 (dd, J = 7.7, 7.7 Hz, 1H), 7.26 (ddd, J = 7.7, 1.9, 0.7 Hz, 1H), 2.48 (s, 3H), 2.40 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 157.5 (CH), 157.0 (CH), 152.7 (C_q), 149.2 (C_q), 140.2 (C_q), 139.1 (C_q), 132.6 (C_q), 132.4 (CH), 132.3 (CH), 131.7 (C_q), 130.1 (CH), 129.1 (CH), 124.2 (CH), 120.1 (CH), 116.5 (CH), 21.4 (CH₃), 21.3 (CH₃).

IR (ATR): 3052, 2918, 1547, 1410, 999, 825, 786, 722, 686, 532 cm^‒1.

MS (EI) m/z (relative intensity): 288 ([M⁺] 29), 261 (35), 142 (29), 115 (32), 91 (100), 65 (35), 43 (86).

HR-MS (EI) m/z for C18H16N4 [M⁺] calcd.: 288.1375.

found: 288.1371.

Synthesis of Methyl (E)-2'-{(3,5-dimethylphenyl)diazenyl}-4'-methyl-[1,1'-biphenyl]-4-carboxylate (83la)

The general procedure D was followed using 13l (224 mg, 1.00 mmol) and methyl 4-bromobenzoate (52a) (108 mg, 0.50 mmol). Purification by column chromatography (n-hexane/CH2Cl2: 7/3) yielded 83la (168 mg, 94%) as an orange solid.

M. p.: 159‒160 °C.

1H-NMR (CDCl₃, 500 MHz): δ = 8.08 (d, J = 8.5 Hz, 2H), 7.54–7.51 (m, 3H), 7.46 (d, J = 7.8 Hz, 1H), 7.39 (s, 2H), 7.35 (dd, J = 7.8, 1.2 Hz, 1H), 7.10–7.07 (m, 1H), 3.94 (s, 3H), 2.46 (s, 3H), 2.35 (s, 6H).

13C-NMR (CDCl₃, 126 MHz): δ = 167.2 (Cq), 153.0 (C_q), 149.6 (C_q), 143.7 (C_q), 138.9 (C_q), 138.7 (Cq), 137.0 (Cq), 132.7 (CH), 131.5 (CH), 130.8 (CH), 130.5 (CH), 128.8 (CH), 128.6 (C_q), 121.0 (CH), 116.3 (CH), 52.1 (CH₃), 21.3 (CH₃), 21.2 (CH₃).

IR (ATR): 2951, 2915, 2854, 1720, 1606, 1438, 1278, 1105, 859, 829, 775, 686 cm^‒1.

MS (EI) m/z (relative intensity): 358 ([M⁺] 61), 343 (59), 299 (27), 225 (36), 165 (72), 105 (100), 77 (25).

HR-MS (ESI) m/z for C23H22N2O2 [M+H⁺] calcd.: 359.1754.

found: 359.1754.

Synthesis of Methyl 2'-amino-4'-methyl-[1,1'-biphenyl]-4-carboxylate (34aa)

The general procedure E was followed using 13a (210 mg, 1.00 mmol), methyl 4-bromobenzoate (52a) (108 mg, 0.50 mmol), Zn (164 mg, 2.50 mmol) and HCl (0.40 mL).

Purification by column chromatography (n-hexane/EtOAc: 5/1) yielded 34aa (101 mg, 84%) as a colorless solid.

M. p.: 136‒137 °C.

1H-NMR (CDCl₃, 300 MHz): δ = 8.08 (d, J = 8.6 Hz, 2H), 7.52 (d, J = 8.6 Hz, 2H), 7.02 (d, J = 7.7 Hz, 1H), 6.65 (ddd, J = 7.7, 1.6, 0.7 Hz, 1H), 6.59 (s, 1H), 3.92 (s, 3H), 3.71 (s, 2H), 2.30 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 166.9 (Cq), 144.5 (Cq), 143.2 (Cq), 139.2 (Cq), 130.2 (CH), 130.0 (CH), 129.0 (CH), 128.6 (Cq), 123.7 (Cq), 119.8 (CH), 116.5 (CH), 52.1 (CH3), 21.2 (CH3).

IR (ATR): 3442, 3360, 2947, 2915, 2164, 1703, 1604, 1435, 1280, 1178, 1103, 772 cm^‒1. MS (EI) m/z (relative intensity): 241 ([M⁺] 100), 210 (31), 167 (35), 84 (24), 49 (38).

HR-MS (EI) m/z for C15H15NO2 [M⁺] calcd.: 241.1103.

found: 241.1109.

Synthesis of N4',N4',4-Trimethyl-[1,1'-biphenyl]-2,4'-diamine (34ae)

The general procedure E was followed using 13a (210 mg, 1.00 mmol), 4-bromo-N,N-dimethylaniline (52e) (100 mg, 0.50 mmol), Zn (164 mg, 2.50 mmol) and HCl (0.40 mL).

Purification by column chromatography (n-hexane/EtOAc: 1/1) yielded 34ae (59 mg, 52%) as a colorless solid.

M. p.: 122‒123 °C.

1H-NMR (CDCl₃, 500 MHz): δ = 7.31 (d, J = 8.8 Hz, 2H), 7.00 (d, J = 7.6 Hz, 1H), 6.81 (d, J = 8.8 Hz, 2H), 6.62 (ddd, J = 7.6, 1.5, 0.6 Hz, 1H), 6.58 (s, 1H), 3.65 (s, 2H), 2.97 (s, 6H), 2.28 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 149.4 (Cq), 143.5 (Cq), 137.6 (Cq), 130.3 (CH), 129.8 (CH), 127.6 (Cq), 125.2 (Cq), 119.5 (CH), 116.2 (CH), 112.9 (CH), 40.7 (CH3), 21.2 (CH3).

IR (ATR): 3443, 3360, 2917, 1605, 1527, 1499, 1219, 1060, 944, 802 cm^‒1. MS (EI) m/z (relative intensity): 226 ([M⁺] 100), 211 (14), 182 (12), 113 (10).

HR-MS (EI) m/z for C15H18N2 [M⁺] calcd.: 226.1470.

found: 226.1465.

Synthesis of 2'-Amino-4'-methyl-[1,1'-biphenyl]-4-carbonitrile (34ai)

The general procedure E was followed using 13a (210 mg, 1.00 mmol), 4-bromobenzonitrile (52i) (91 mg, 0.50 mmol), Zn (164 mg, 2.50 mmol) and HCl (0.40 mL). Purification by column chromatography (n-hexane/EtOAc: 5/1) yielded 34ai (64 mg, 61%) as a colorless solid.

M. p.: 121‒122 °C.

1H-NMR (CDCl₃, 500 MHz): δ = 7.69 (d, J = 8.6 Hz, 2H), 7.57 (d, J = 8.6 Hz, 2H), 6.98 (d, J = 7.7 Hz, 1H), 6.66 (ddd, J = 7.7, 1.6, 0.7 Hz, 1H), 6.60 (s, 1H), 3.75 (s, 2H), 2.30 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 144.6 (Cq), 143.0 (C_q), 139.7 (C_q), 132.5 (CH), 130.1 (CH), 129.8 (CH), 122.8 (Cq), 120.1 (CH), 118.9 (Cq), 116.7 (CH), 110.5 (Cq), 21.2 (CH3).

IR (ATR): 3441, 3363, 2297, 2228, 1618, 1512, 1490, 1399, 1170, 1003, 843 cm^‒1. MS (EI) m/z (relative intensity): 208 ([M⁺] 100), 192 (19), 43 (10).

HR-MS (EI) m/z for C14H12N2 [M⁺] calcd.: 208.1000.

found: 208.0999.

Synthesis of 3',4',5'-Trimethoxy-4-methyl-[1,1'-biphenyl]-2-amine (34al)

The general procedure E was followed using 13a (210 mg, 1.00 mmol), 5-bromo-1,2,3-trimethoxybenzene (52l) (124 mg, 0.50 mmol), Zn (164 mg, 2.50 mmol) and HCl (0.40 mL).

Purification by column chromatography (n-hexane/EtOAc: 1/1) yielded 34al (115 mg, 84%) as a colorless solid.

M. p.: 136‒137 °C.

1H-NMR (CDCl₃, 500 MHz): δ = 7.02 (d, J = 7.6 Hz, 1H), 6.64 (s, 2H), 6.63 (dd, J = 7.7, 0.6 Hz, 1H), 6.59 (s, 1H), 3.88 (s, 3H), 3.85 (s, 6H), 3.73 (s, 2H), 2.29 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 153.3 (Cq), 143.2 (C_q), 138.4 (C_q), 136.9 (C_q), 135.0 (C_q), 130.0 (CH), 124.9 (Cq), 119.4 (CH), 116.2 (CH), 106.1 (CH), 60.8 (CH3), 56.1 (CH3), 21.1 (CH3).

IR (ATR): 3421, 3350, 2960, 2834, 1583, 1449, 1237, 1117, 1025, 834 cm^‒1.

MS (EI) m/z (relative intensity): 273 ([M⁺] 100), 258 (71), 198 (14), 144 (16), 43 (12).

HR-MS (EI) m/z for C16H19NO3 [M⁺] calcd.: 273.1365.

found: 273.1372.

Synthesis of 3',4'-Dichloro-4-methyl-[1,1'-biphenyl]-2-amine (34am)

The general procedure E was followed using 13a (210 mg, 1.00 mmol), 4-bromo-1,2-dichlorobenzene (52m) (113 mg, 0.50 mmol), Zn (164 mg, 2.50 mmol) and HCl (0.40 mL).

Purification by column chromatography (n-hexane/EtOAc: 5/1) yielded 34am (76 mg, 60%) as a colorless solid.

M. p.: 125‒126 °C.

1H-NMR (DMSO-d₆, 300 MHz): δ = 7.64 (d, J = 8.3 Hz, 1H), 7.59 (d, J = 2.1 Hz, 1H), 7.37 (dd, J = 8.3, 2.1 Hz, 1H), 6.88 (d, J = 7.8 Hz, 1H), 6.58 (s, 1H), 6.46 (ddd, J = 7.8, 1.3, 0.6 Hz, 1H), 4.82 (s, 2H), 2.19 (s, 3H).

13C-NMR (DMSO-d6, 126 MHz): δ = 144.9 (Cq), 140.5 (Cq), 138.1 (Cq), 131.1 (Cq), 130.6 (CH), 130.4 (CH), 129.8 (CH), 129.0 (CH), 128.9 (Cq), 120.5 (Cq), 117.8 (CH), 116.0 (CH), 20.8 (CH3).

IR (ATR): 3462, 3376, 2922, 2853, 1616, 1465, 1373, 1132, 1029, 827 cm^‒1.

MS (EI) m/z (relative intensity): 251 ([M⁺] 100), 215 (24), 181 (35), 84 (27), 58 (18).

HR-MS (EI) m/z for C13H11Cl2N [M⁺] calcd.: 251.0269.

found: 251.0264.

Synthesis of Methyl 2'-(1-benzyl-1H-tetrazol-5-yl)-[1,1'-biphenyl]-4-carboxylate (69aa) and Dimethyl 2'-(1-benzyl-1H-tetrazol-5-yl)-[1,1':3',1''-terphenyl]-4,4''-dicarboxylate (69aa')

The general procedure F was followed using 68a (70.9 mg, 0.30 mmol) and methyl 4-chlorobenzoate (59a) (154 mg, 0.90 mmol). Purification by column chromatography (n-hexane/EtOAc: 4/1) yielded 69aa (86 mg, 77%) and 69aa' (15 mg, 10%) as colorless solids.

M. p.: 109–110 °C.

1H-NMR (CDCl3, 500 MHz): 7.90 (d, J = 8.4 Hz, 2H), 7.64 (ddd, J = 7.6, 7.6, 1.4 Hz, 1H), 7.56 (dd, J = 7.9, 0.9 Hz, 1H), 7.46 (ddd, J = 7.6, 7.6, 1.4 Hz, 1H), 7.35 (dd, J = 7.9, 0.9 Hz, 1H), 7.19 (tt, J = 7.4, 1.8 Hz, 1H), 7.15‒7.10 (m, 4H), 6.75 (d, J = 8.4 Hz, 2H), 4.83 (s, 2H), 3.90 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 166.4 (Cq), 154.2 (Cq), 143.2 (Cq), 140.7 (Cq), 132.9 (Cq), 131.6 (CH), 131.2 (CH), 130.2 (CH), 130.0 (CH), 129.6 (Cq), 128.8 (CH), 128.7 (CH), 128.6 (CH), 128.5 (CH), 127.7 (CH), 122.7 (C_q), 52.3 (CH₃), 50.9 (CH₂).

IR (ATR): 2951, 1717, 1435, 1403, 1278, 1103, 1007, 911, 753, 723 cm^‒1.

MS (EI) m/z (relative intensity): 370 ([M⁺] 19), 369 (58), 341 (14), 164 (17), 91 (100), 65 (14).

HR-MS (ESI) m/z for C₂₂H₁₉N₄O₂ [M+H⁺] calcd.: 371.1503.

found: 371.1503.

M. p.: 180–181 °C.

1H-NMR (CDCl3, 500 MHz): 7.82 (d, J = 8.6 Hz, 4H), 7.73 (t, J = 7.8 Hz, 1H), 7.52 (d, J = 7.8 Hz, 2H), 7.24 (tt, J = 7.8, 1.2 Hz, 1H), 7.13 (dd, J = 7.8, 7.8 Hz, 2H), 6.99 (d, J = 8.6 Hz, 4H), 6.68 (dd, J = 7.8, 1.2 Hz, 2H), 4.69 (s, 2H), 3.88 (s, 6H).

13C-NMR (CDCl3, 126 MHz): δ = 166.5 (Cq), 152.3 (Cq), 143.1 (Cq), 142.7 (Cq), 132.3 (Cq), 131.5 (CH), 130.0 (CH), 129.6 (CH), 129.5 (C_q), 129.0 (CH), 128.9 (CH), 128.8 (CH), 128.1 (CH), 121.3 (C_q), 52.2 (CH₃), 50.8 (CH₂).

IR (ATR): 2951, 1719, 1433, 1271, 1100, 1017, 864, 769, 721, 704 cm^‒1.

MS (EI) m/z (relative intensity): 504 ([M⁺] 44), 503 (51), 325 (23), 239 (27), 91 (100), 58 (33).

HR-MS (ESI) m/z for C30H25N4O4 [M+H⁺] calcd.: 505.1870.

found: 505.1868.

Synthesis of Methyl 2'-(1-benzyl-1H-tetrazol-5-yl)-4'-methyl-[1,1'-biphenyl]-4-carboxylate (69ca)

The general procedure F was followed using 68c (75.1 mg, 0.30 mmol) and methyl 4-chlorobenzoate (59a) (154 mg, 0.90 mmol). Purification by column chromatography (CH₂Cl₂/EtOAc: 24/1) yielded 69ca (103 mg, 89%) as a colorless solid.

M. p.: 111–112 °C.

1H-NMR (CDCl₃, 300 MHz): δ = 7.87 (d, J = 8.4 Hz, 2H), 7.46‒7.39 (m, 2H), 7.21‒7.05 (m, 6H), 6.73 (d, J = 8.4 Hz, 2H), 4.79 (s, 2H), 3.87 (s, 3H), 2.35 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 166.3 (Cq), 154.3 (C_q), 143.2 (C_q), 138.6 (C_q), 137.8 (C_q), 132.9 (Cq), 132.3 (CH), 131.7 (CH), 130.1 (CH), 129.9 (CH), 129.4 (Cq), 128.6 (CH), 128.5 (CH), 128.4 (CH), 127.6 (CH), 122.5 (Cq), 52.2 (CH3), 50.9 (CH2), 20.9 (CH3).

IR (ATR): 2951, 1712, 1606, 1434, 1275, 1185, 866, 823, 776, 727 cm^‒1.

MS (EI) m/z (relative intensity): 384 ([M⁺] 27), 383 (71), 355 (19), 178 (15), 91 (100), 65 (14).

HR-MS (EI) m/z for C23H20N4O2 [M⁺] calcd.: 384.1586.

found: 384.1574.

Synthesis of Methyl 2'-(1-benzyl-1H-tetrazol-5-yl)-5'-methyl-[1,1'-biphenyl]-4-carboxylate (69da) and Dimethyl 2'-(1-benzyl-1H-tetrazol-5-yl)-5'-methyl-[1,1':3',1''-terphenyl]-4,4''-dicarboxylate (69da')

The general procedure F was followed using 68d (75.1 mg, 0.30 mmol) and methyl 4-chlorobenzoate (59a) (154 mg, 0.90 mmol). Purification by column chromatography (CH2Cl2/EtOAc: 24/1) yielded 69da (72 mg, 62%) and 69da' (24 mg, 15%) as colorless solids.

M. p.: 125–126 °C.

1H-NMR (CDCl3, 300 MHz): 7.88 (d, J = 8.4 Hz, 2H), 7.36 (s, 1H), 7.30‒7.08 (m, 7H), 7.16 (d, J = 8.4 Hz, 2H), 4.81 (s, 2H), 3.89 (s, 3H), 2.47 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 166.3 (Cq), 154.2 (Cq), 143.3 (Cq), 141.9 (Cq), 140.5 (Cq), 132.9 (Cq), 131.0 (CH), 130.9 (CH), 129.9 (CH), 129.5 (Cq), 129.1 (CH), 128.6 (CH), 128.5 (CH), 128.4 (CH), 127.6 (CH), 119.7 (Cq), 52.2 (CH2), 50.8 (CH3), 21.5 (CH3).

IR (ATR): 2951, 1718, 1435, 1277, 1182, 1102, 859, 823, 721, 705 cm^‒1.

MS (EI) m/z (relative intensity): 384 ([M⁺] 31), 383 (76), 355 (23), 178 (19), 91 (100), 65 (14), 43 (19).

HR-MS (ESI) m/z for C₂₃H₂₁N₄O₂ [M+H⁺] calcd.: 385.1659.

found: 385.1663.

M. p.: 194–195 °C.

1H-NMR (CDCl3, 300 MHz): 7.80 (d, J = 8.6 Hz, 4H), 7.33 (s, 2H), 7.22 (tt, J = 7.4, 1.4 Hz, 1H), 7.12 (dd, J = 7.6, 7.6 Hz, 2H), 6.99 (d, J = 8.6 Hz, 4H), 6.68 (dd, J = 7.8, 1.2 Hz, 2H), 4.67 (s, 2H), 3.87 (s, 6H), 2.53 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 166.3 (C_q), 152.3 (C_q), 143.2 (C_q), 142.4 (C_q), 141.7 (C_q), 132.4 (Cq), 130.6 (CH), 129.4 (CH), 129.3 (Cq), 128.8 (CH), 128.7 (CH), 128.6 (CH), 127.9 (CH), 118.3 (C_q), 52.2 (CH₃), 50.7 (CH₂), 21.5 (CH₃).

IR (ATR): 2949, 1711, 1610, 1435, 1269, 1183, 1110, 1017, 856, 723 cm^‒1.

MS (EI) m/z (relative intensity): 518 ([M⁺] 67), 517 (84), 339 (23), 253 (27), 91 (100), 43 (51).

HR-MS (ESI) m/z for C31H27N4O4 [M+H⁺] calcd.: 519.2027.

found: 519.2015.

Synthesis of Methyl 2'-(1-benzyl-1H-tetrazol-5-yl)-4'-methoxy-[1,1'-biphenyl]-4-carboxylate (69ea) and Methyl 2'-(1-benzyl-1H-tetrazol-5-yl)-6'-methoxy-[1,1'-biphenyl]-4-carboxylate (69ea'')

The general procedure F was followed using 68e (79.9 mg, 0.30 mmol) and methyl 4-chlorobenzoate (59a) (154 mg, 0.90 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 69ea (71 mg, 59%) and 69ea'' (11 mg, 9%) as colorless solids.

M. p.: 128–129 °C.

1H-NMR (CDCl3, 300 MHz): 7.89 (d, J = 8.4 Hz, 2H), 7.48 (d, J = 8.6 Hz, 1H), 7.20‒7.08 (m, 6H), 6.80 (d, J = 2.7 Hz, 1H), 6.75 (d, J = 8.4 Hz, 2H), 4.80 (s, 2H), 3.88 (s, 3H), 3.75 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 166.5 (C_q), 159.4 (C_q), 154.2 (C_q), 143.0 (C_q), 132.9 (C_q), 132.8 (C_q), 131.5 (CH), 130.0 (CH), 129.1 (C_q), 128.7 (CH), 128.6 (CH), 128.5 (CH), 127.7 (CH), 123.7 (C_q), 118.0 (CH), 115.7 (CH), 55.6 (CH₃), 52.2 (CH₃), 50.9 (CH₂).

IR (ATR): 2951, 1716, 1607, 1435, 1274, 1224, 1103, 1023, 826, 719 cm^‒1.

MS (EI) m/z (relative intensity): 400 ([M⁺] 17), 399 (42), 371 (12), 91 (100), 65 (13).

HR-MS (ESI) m/z for C23H21N4O3 [M+H⁺] calcd.: 401.1608.

found: 401.1610.

M. p.: 121–122 °C.

1H-NMR (CDCl3, 500 MHz): 7.86 (d, J = 8.4 Hz, 2H), 7.43 (dd, J = 8.4, 7.7 Hz, 1H), 7.22 (tt, J = 7.4, 1.4 Hz, 1H), 7.20‒7.15 (m, 3H), 7.11 (d, J = 8.4 Hz, 2H), 6.93 (dd, J = 7.7, 1.0 Hz, 1H), 6.83 (dd, J = 8.4, 1.4 Hz, 2H), 4.91 (s, 2H), 3.88 (s, 3H), 3.80 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 166.6 (C_q), 156.8 (C_q), 153.8 (C_q), 139.1 (C_q), 133.1 (C_q), 130.3 (CH), 130.0 (C_q), 129.7 (CH), 129.3 (C_q), 129.2 (CH), 128.8 (CH), 128.7 (CH), 127.8 (CH), 124.8 (C_q), 122.8 (CH), 113.8 (CH), 56.0 (CH₃), 52.2 (CH₃), 50.9 (CH₂).

IR (ATR): 2952, 1713, 1609, 1460, 1263, 1101, 1027, 801, 774, 754 cm^‒1.

MS (EI) m/z (relative intensity): 400 ([M⁺] 40), 399 (83), 371 (17), 91 (100), 65 (12).

HR-MS (ESI) m/z for C23H21N4O3 [M+H⁺] calcd.: 401.1608.

found: 401.1600.

Synthesis of Methyl 2'-(1-benzyl-1H-tetrazol-5-yl)-5'-methoxy-[1,1'-biphenyl]-4-carboxylate (69fa) and Dimethyl 2'-(1-benzyl-1H-tetrazol-5-yl)-5'-methoxy-[1,1':3',1''-terphenyl]-4,4''-dicarboxylate (69fa')

The general procedure F was followed using 68f (79.9 mg, 0.30 mmol) and methyl 4-chlorobenzoate (59a) (154 mg, 0.90 mmol). Purification by column chromatography (CH2Cl2/EtOAc: 24/1) yielded 69fa (84 mg, 70%) and 69fa' (19 mg, 12%) as colorless solids.

M. p.: 143–144 °C.

1H-NMR (CDCl3, 300 MHz): 7.88 (d, J = 8.4 Hz, 2H), 7.27 (d, J = 8.5 Hz, 1H), 7.18 (tt, J = 7.4, 1.4 Hz, 1H), 7.15‒7.20 (m, 4H), 7.04 (d, J = 2.6 Hz, 1H), 6.97 (dd, J = 8.5, 2.6 Hz, 1H), 6.76 (d, J = 8.4 Hz, 2H), 4.81 (s, 2H), 3.89 (s, 3H), 3.88 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 166.4 (Cq), 161.8 (Cq), 154.1 (Cq), 143.2 (Cq), 142.3 (Cq), 133.0 (Cq), 132.6 (CH), 130.0 (CH), 129.6 (Cq), 128.7 (CH), 128.6 (CH), 128.5 (CH), 127.6 (CH), 115.8 (CH), 114.5 (Cq), 113.8 (CH), 55.6 (CH3), 52.2 (CH3), 50.7 (CH2).

IR (ATR): 2947, 1720, 1607, 1436, 1288, 1213, 1107, 1012, 855, 725 cm^‒1.

MS (EI) m/z (relative intensity): 400 ([M⁺] 22), 399 (62), 371 (23), 91 (100), 65 (14).

HR-MS (ESI) m/z for C₂₃H₂₁N₄O₃ [M+H⁺] calcd.: 401.1608.

found: 401.1610.

M. p.: 179–180 °C.

1H-NMR (CDCl₃, 300 MHz): 7.81 (d, J = 8.6 Hz, 4H), 7.18‒7.10 (m, 3H), 7.02 (s, 2H), 7.00‒6.97 (m, 4H), 6.70 (dd, J = 7.8, 1.2 Hz, 2H), 4.67 (s, 2H), 3.94 (s, 3H), 3.88 (s, 6H).

13C-NMR (CDCl3, 126 MHz): δ = 166.3 (Cq), 161.2 (Cq), 152.3 (Cq), 144.2 (Cq), 143.1 (Cq), 132.5 (Cq), 129.5 (Cq), 129.4 (CH), 128.8 (CH), 128.7 (CH), 128.5 (CH), 128.0 (CH), 115.4 (CH), 113.3 (Cq), 55.8 (CH3), 52.2 (CH3), 50.7 (CH2).

IR (ATR): 2949, 1717, 1594, 1434, 1272, 1178, 1100, 1016, 854, 723 cm^‒1.

MS (EI) m/z (relative intensity): 534 ([M⁺] 51), 533 (73), 339 (13), 91 (100), 58 (55).

HR-MS (ESI) m/z for C31H27N4O5 [M+H⁺] calcd.: 535.1976.

found: 535.1975.

Synthesis of Methyl 4-{3-(1-benzyl-1H-tetrazol-5-yl)naphthalen-2-yl}benzoate (69ga)

The general procedure F was followed using 68g (85.9 mg, 0.30 mmol) and methyl 4-chlorobenzoate (59a) (154 mg, 0.90 mmol). Purification by column chromatography (n-hexane/EtOAc: 7/3) yielded 69ga (72 mg, 57%) as a colorless solid.

M. p.: 162–163 °C.

1H-NMR (CDCl3, 500 MHz): δ = 8.03 (s, 1H), 7.96 (dd, J = 8.3, 1.2 Hz, 1H), 7.93 (d, J = 8.3 Hz, 2H), 7.91 (s, 1H), 7.84 (dd, J = 8.3, 1.2 Hz, 1H), 7.65 (ddd, J = 8.2, 6.9, 1.3 Hz, 1H), 7.60 (ddd, J = 8.2, 6.9, 1.3 Hz, 1H), 7.24 (d, J = 8.3 Hz, 2H), 7.15 (tt, J = 7.4, 1.3 Hz, 1H), 7.08 (dd, J = 7.3, 7.2 Hz, 2H), 6.75 (dd, J = 8.1, 1.3 Hz, 2H), 4.89 (s, 2H), 3.91 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 166.5 (C_q), 154.4 (C_q), 143.4 (C_q), 137.0 (C_q), 134.2 (C_q), 132.9 (C_q), 132.1 (CH), 132.0 (C_q), 130.1 (CH), 129.8 (CH), 129.5 (C_q), 128.8 (CH), 128.7 (CH), 128.6 (CH), 128.5 (CH), 128.2 (CH), 128.1 (CH), 127.7 (CH), 127.6 (CH), 120.5 (C_q), 52.3 (CH₃), 51.0 (CH₂).

IR (ATR): 2951, 1708, 1606, 1430, 1277, 1100, 900, 777, 732, 477 cm^‒1.

MS (EI) m/z (relative intensity): 420 ([M⁺] 20), 419 (40), 207 (38), 91 (100), 73 (25), 65 (12).

HR-MS (ESI) m/z for C26H21N4O2 [M+H⁺] calcd.: 421.1659.

found: 421.1655.

Synthesis of 1-{2'-(1-Benzyl-1H-tetrazol-5-yl)-4'-methyl-[1,1'-biphenyl]-4-yl}ethan-1-one (69cb)

The general procedure F was followed using 68c (75.1 mg, 0.30 mmol) and 1-(4-chlorophenyl)ethan-1-one (59b) (139 mg, 0.90 mmol). Purification by column chromatography (n-hexane/EtOAc: 4/1) yielded 69cb (92 mg, 83%) as a colorless solid.

M. p.: 128–129 °C.

1H-NMR (CDCl3, 500 MHz): δ = 7.79 (d, J = 8.5 Hz, 2H), 7.44 (s, 1H), 7.44 (s, 1H), 7.18 (tt, J = 7.3, 1.3 Hz, 1H), 7.16‒7.10 (m, 5H), 6.74 (dd, J = 8.1, 1.3 Hz, 2H), 4.83 (s, 2H), 2.54 (s, 3H), 2.36 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 197.3 (Cq), 154.3 (Cq), 143.4 (Cq), 138.7 (Cq), 137.7 (Cq), 136.0 (Cq), 132.9 (Cq), 132.4 (CH), 131.7 (CH), 130.1 (CH), 128.8 (CH), 128.7 (CH), 128.6 (CH), 128.5 (CH), 127.7 (CH), 122.4 (Cq), 50.9 (CH2), 26.6 (CH3), 20.9 (CH3).

IR (ATR): 2921, 1679, 1605, 1403, 1357, 1265, 1101, 957, 821, 719 cm^‒1.

MS (EI) m/z (relative intensity): 368 ([M⁺] 35), 367 (87), 339 (22), 178 (17), 91 (100), 65 (12), 43 (19).

HR-MS (ESI) m/z for C23H21N4O [M+H⁺] calcd.: 369.1710.

found: 369.1707.

The analytical data are in accordance with those reported in the literature.^[118]

Synthesis of 1-Benzyl-5-(4'-methoxy-4-methyl-[1,1'-biphenyl]-2-yl)-1H-tetrazole (69cc)

The general procedure F was followed using 68c (75.1 mg, 0.30 mmol) and 1-chloro-4-methoxybenzene (59c) (128 mg, 0.90 mmol). Purification by column chromatography (n-hexane/EtOAc: 4/1) yielded 69cc (90 mg, 84%) as a colorless solid.

M. p.: 121–122 °C.

1H-NMR (CDCl3, 500 MHz): δ = 7.40 (d, J = 7.9 Hz, 1H), 7.37 (dd, J = 8.1, 1.3 Hz, 1H), 7.16 (tt, J = 7.3, 1.3 Hz, 1H), 7.12 (d, J = 7.6 Hz, 2H), 7.10 (s, 1H), 7.02 (d, J = 8.7 Hz, 2H), 6.77 (d, J = 8.7 Hz, 2H), 6.73 (dd, J = 8.1, 1.3 Hz, 2H), 4.74 (s, 2H), 3.75 (s, 3H), 2.32 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 159.2 (Cq), 154.9 (Cq), 138.3 (Cq), 137.3 (Cq), 133.1 (Cq), 132.2 (CH), 131.6 (CH), 131.0 (Cq), 129.9 (CH), 129.6 (CH), 128.5 (CH), 128.3 (CH), 127.8 (CH), 122.1 (Cq), 114.3 (CH), 55.2 (CH3), 50.7 (CH2), 20.7 (CH3).

IR (ATR): 2941, 1610, 1484, 1450, 1249, 1180, 1099, 1033, 852, 721 cm^‒1.

MS (EI) m/z (relative intensity): 356 ([M⁺] 37), 355 (71), 327 (28), 165 (16), 91 (100), 65 (12).

HR-MS (ESI) m/z for C₂₂H₂₁N₄O [M+H⁺] calcd.: 357.1710.

found: 357.1707.

Synthesis of 1-Benzyl-5-{4-methyl-4'-(methylthio)-[1,1'-biphenyl]-2-yl}-1H-tetrazole (69cd)

The general procedure F was followed using 68c (75.1 mg, 0.30 mmol) and (4-chlorophenyl)(methyl)sulfane (59d) (143 mg, 0.90 mmol). Purification by column chromatography (CH₂Cl₂/EtOAc: 24/1) yielded 69cd (71 mg, 64%) as a pale yellow solid.

M. p.: 116–117 °C.

1H-NMR (CDCl₃, 400 MHz): δ = 7.41 (d, J = 0.7 Hz, 1H), 7.40 (dd, J = 1.7, 0.6 Hz, 1H), 7.18 (tt, J = 7.3, 1.3 Hz, 1H), 7.14 (dd, J = 7.4, 5.6 Hz, 2H), 7.13‒7.11 (m, 1H), 7.10 (d, J = 8.7 Hz, 2H), 7.01 (d, J = 8.7 Hz, 2H), 6.73 (dd, J = 8.1, 1.3 Hz, 2H), 4.78 (s, 2H), 2.44 (s, 3H), 2.34 (s, 3H).

13C-NMR (CDCl3, 126 MHz): δ = 154.7 (Cq), 138.8 (Cq), 138.1 (Cq), 137.8 (Cq), 135.1 (Cq), 133.0 (Cq), 132.3 (CH), 131.7 (CH), 129.9 (CH), 128.8 (CH), 128.6 (CH), 128.4 (CH), 127.8 (CH), 126.3 (CH), 122.2 (Cq), 50.8 (CH2), 20.8 (CH3), 15.2 (CH3).

IR (ATR): 2921, 1477, 1439, 1241, 1092, 812, 722, 694, 548, 527 cm^‒1.

MS (EI) m/z (relative intensity): 372 ([M⁺] 61), 371 (42), 343 (20), 206 (14), 91 (100), 65 (11), 43 (11).

HR-MS (EI) m/z for C22H20N4S [M⁺] calcd.: 372.1409.

found: 372.1414.

Synthesis of 1-Benzyl-5-{5-methyl-2-(thiophen-3-yl)phenyl}-1H-tetrazole (69ce)

The general procedure F was followed using 68c (75.1 mg, 0.30 mmol) and 3-chlorothiophene (59e) (107 mg, 0.90 mmol). Purification by column chromatography (n-hexane/EtOAc: 6/1) yielded 69ce (67 mg, 67%) as a pale yellow solid.

M. p.: 96–97 °C.

1H-NMR (CDCl₃, 500 MHz): δ = 7.48 (d, J = 7.9 Hz, 1H), 7.37 (dq, J = 7.9, 0.8 Hz, 1H), 7.24 (q, J = 3.0 Hz, 1H), 7.18 (tt, J = 7.3, 1.3 Hz, 1H), 7.16‒7.12 (m, 2H), 7.09‒7.07 (m, 1H), 6.95 (dd, J = 3.0, 1.4 Hz, 1H), 6.79‒6.75 (m, 3H), 4.81 (s, 2H), 2.33 (s, 3H).

13C-NMR (CDCl₃, 126 MHz): δ = 154.7 (Cq), 139.4 (C_q), 137.8 (C_q), 133.5 (C_q), 133.0 (C_q), 132.3 (CH), 131.6 (CH), 129.6 (CH), 128.6 (CH), 128.5 (CH), 127.9 (CH), 127.4 (CH), 126.7 (CH), 123.2 (CH), 122.1 (Cq), 50.8 (CH2), 20.8 (CH3).

IR (ATR): 2954, 1482, 1409, 1243, 1103, 853, 802, 728, 695, 647 cm^‒1.

MS (EI) m/z (relative intensity): 332 ([M⁺] 26), 213 (24), 198 (20), 185 (42), 91 (100), 65 (25), 43 (18).

HR-MS (EI) m/z for C19H16N4S [M⁺] calcd.: 332.1096.

found: 332.1097.

Synthesis of Methyl N-{[2'-(1-benzyl-1H-tetrazol-5-yl)-[1,1'-biphenyl]-4-yl]methyl}-N-pentanoyl-L-valinate (69at)

The general procedure F was followed using 68a (70.9 mg, 0.30 mmol) and aryl chloride 59t (306 mg, 0.90 mmol). Purification by column chromatography (n-hexane/EtOAc: 4/1) yielded 69at (117 mg, 72%) as a colorless solid.

Alternatively the general procedure F was followed with 68a (70.9 mg, 0.30 mmol) and aryl bromide 52t (127 mg, 0.33 mmol). Purification by column chromatography (n-hexane/EtOAc: 4/1) yielded 60at (144 mg, 89%) as a colorless solid.

M. p.: 74–75 °C.

MS (EI) m/z (relative intensity): 539 ([M⁺] 5), 454 (83), 396 (22), 340 (69), 325 (38), 192 (25), 91 (100), 57 (29).

HR-MS (EI) m/z for C32H37N5O3 [M⁺] calcd.: 539.2896.

found: 539.2894.

The analytical data are in accordance with those reported in the literature.^[131]

Im Dokument Ruthenium(II)-Catalyzed C-H Arylations of Arenes (Seite 98-176)